Sheet - 01 - Thermochemistry

(Physical Chemistry) THERMOCHEMISTRY
THERMOCHEMISTRY
Thermochemistry is the branch of physical chemistry which deals with the thermal or heat
changes caused by chemical reactions. It is based on first law of thermodynamics.
1. ENTHALPY OF A SUBSTANCE :
⚫ Every substance has a fixed value of enthalpy under any particular state. Though, its exact value
cannot be calculated but it has some finite fixed value.
⚫ The enthalpy of one mole of a substance called molar enthalpy in any particular state can be
assigned symbol
⚫ Hm(substance) : For example molar enthalpy of water vapours at 398 K and 1 atm pressure may
be represented as Hm (H2O, g, 398 K, 1 atm). In very simple words, enthalpy can be considered
as heat constant (amount) of substance, and during reaction this heat is being released or
absorbed.
⚫ Molar enthalpy of substance under standard conditions is called standard molar enthalpy of a
substance. Standard state of any substance means.
 For a GAS standard state means ideal gas at 1 bar partial pressure at any give
temperature.
 For a LIQUID – pure liquid at one bar pressure at 1 bar pressure at any given temperature.
 For a PURE CRYSTALLINE SOLID – pure crystalline solid at 1 bar pressure and at any
given temperature
 For any SUBSTANCE or ION IN SOLUTION – the species should be in unit molality (can
also be taken as 1M concentration), at one bar pressure and at any given temperature.
⚫ Molar standard enthalpy of water vapours at 398 K will be represented as H°(H2O, g , 398 K) and
molar standard enthalpy of liquid water at 398 K will be represented as Hm°(H2O, l, 398 K)
(It is hypothetical but can be calculated).
⚫ We cannot exactly calculate enthalpy content of a substance only the change in enthalpy can be
calculated when substance is taken from one state to other.
For example :
Let enthalpy content initially be H0m,1 & finally enthalpy content be H0m,2
Then, H° = H0m,2 − H0m,1
= heat added at constant pressure to change temperature from 25°C to 50°C.
= CPT = (18 cal/mole °C) (25°C) = 450 cal
2. ENTHALPY CHANGE OF REACTION, (rH)
The enthalpy change accompanying a reaction is called the reaction enthalpy. It may also be
defined as the amount of heat lost or gained in the chemical reaction, when all the
reactants and products are maintained at the same temperature and pressure. The enthalpy
change of a chemical reaction may be given as
rH = (sum of enthalpies of products)-(sum of enthalpy of reactants)
APNI KAKSHA 1
=  (H)products –  (H)reactants
1. Why does heat get released/absorbed during chemical reactions?

Sol. Because the reactants have a fixed enthalpy content before the reaction and when these are
converted into the products which have a different enthalpy content. So, heat gets released or
absorbed. Even if temperature of reactions remains constant yet due to change in bonding
energies U  0.
If Hproducts > Hreactants
Reaction should be endothermic as we have to give extra heat to reactants to get these converted
into products
and if Hproducts < Hreactants
Reaction will be exothermic as extra heat content of reactants will be released during the
reaction.
Enthalpy change of a reaction : Hreaction = Hproducts – Hreactants
H°reactions = H°products – H°reactants
= positive : endothermic
= negative : exothermic
3. FACTORS AFFECTING H OF THE REACTIONS ARE :

(i) Physical states of reactants & products.
(ii) Allotropic forms of elements.
(iii) Reaction conditions.
H = U + ngRT
where H = Heat change of reaction at constant pressure or enthalpy change.
U = Heat change of reaction at constant volume or internal energy change.
ng = Total moles of gaseous products – total moles of gaseous reactants.
It should be noted that while computing ng of a reaction, only the stoichiometric numbers of
gaseous is counted and those of liquids and solids are completely ignored.
(iv) Temperature : Variation of Hº with temperature can be explained by Kirchoff’s equation.
 r H2° =  r H1° +   r CP .dT
 r CP =  ( C p ) products –  ( Cp )
reac tan ts
= Difference in molar heat capacities of products and reactants.

For example for the reaction
N2 (g) + 3H2 (g) ⎯→ 2NH3 (g)
 r H2° =  r H1° +  r CP (T2 – T1)
where  r CP = 2CP,NH − CP,N − 3CP,H
3 2 2
* for a constant volume reaction, E02 = E10 +   r CV .dT

2. The molar heat capacities at constant pressure (assumed constant with respect to temperature)
at A,B and C are in ratio of 3 : 1.5 : 2.0 The enthalpy change for the exothermic reaction A + 2B →
3C at 300 K and 310 K is  r H300 and  r H 310 respectively then :
APNI KAKSHA 2
(A)  r H 300 >  r H 310

(B)  r H 300 <  r H 310
(C)  r H 300 =  r H 310
(D) if T2 > T1 then  r H 310 >  r H 300 and if T2 < T1 then  r H 310 <  r H 300
Ans. (C)
Sol. rC p = 0,   r H 300 =  r H 310
4. THERMOCHEMICAL EQUATIONS :
An equation which indicates the amount of heat change in the reaction. These can be added,
subtracted or multiplied whenever required. It indicates the amount of heat change in the
reaction, which is written on the extreme right of the reaction. for example :
aA(g) + bB(g) → cC(g) + dD(g) H = ± x kJ mol–1
5. TYPES OF ENTHALPY CHANGES IN CHEMICAL REACTIONS :
5.1 STANDARD ENTHALPY OF FORMATION :

It is not possible to determine the absolute value of the molar enthalpy of a substance. However,
based on the following convention, the relative values of standard molar enthalpies of formation
of various substances can be built.
⚫ “The standard enthalpy of formation of every element in its stable state of aggregation at one bar
pressure and at specified temperature is assigned a zero value”.The specified temperature is
usually taken as 25°C.
A few exmaples are Hf° (O2 , g) = 0
Hf° (C, graphite) = 0 Hf° (C, diamond)  0
Hf° (Br2 , liquid) = 0
Hf° (S, rhombic) = 0 Hf° (S, monoclinic)  0
Hf° (P, white) = 0 Hf° (P, black)  0
⚫ “The standard enthalpy of formation of a compound is the change in the standard enthalpy when
one mole of the compound is formed from its constituent elements taken in their standard or
reference state”.
The chemical equations corresponding to enthalpy of formation of few substances are given
below.
1 1
Enthalpy of formation of HBr(g) : H2 (g) + Br2 (l) → HBr(g)
2 2
1 1
Hf°(HBr, g) = H 0m (HBr, g) – H 0m (H2, g) – H 0m (Br2, l) ...(1)
2 2
Enthalpy of formation of SO2 (g) : S (rhombic) + O2 (g) → SO2 (g)
Hf° (SO2, g) = H 0m (SO2, g) – H 0m (S, rhombic) – H 0m (O2, g) ...(B)
But above equations cannot be for calculation of enthalpy of reaction as the molar enthalpies of
different species can not be exactly known.
APNI KAKSHA 3
5.1.1 ENTHALPY OF REACTION FROM ENTHALPIES OF

FORMATION:
The enthalpy of reaction can be calculated by
Hr° =  B Hf°,products –  B Hf°,reactants
B is the stoichiometric coefficient
above equation holds good for any
reaction as the same reference state is
used for reactants and products
(shown in figure).
3. Calculate the standard enthalpy of reaction ZnO(s) + CO(g) ⎯→ Zn(s) + CO2 (g).
Given, Hf°(ZnO, s) = –350 KJ/mole, Hf°(CO2, g) = –390 KJ/mole,
Hf° (CO, g) = – 110 KJ/mole.
Ans. 7kJ.
Sol. H° = {Hf°(CO2, g) – (Hf° (ZnO, s) + Hf° (CO, g))}
H°reaction = –390 –(–350 –110) = 70 kJ
5.1.2 HESS’S LAW OF CONSTANT HEAT SUMMATION :

⚫ The heat absorbed or evolved in a given chemical equation is the same whether the process
occurs in one step or several steps.
⚫ The chemical equation can be treated as ordinary algebraic expressions and can be added or
subtracted to yield the required equation. The corresponding enthalpies of reactions are also
manipulated in the same way so as to give the enthalpy of reaction for the desired chemical
equation.
⚫ Since rH stands for the change of enthalpy when reactants (substances on the left hand side of
the arrow) are converted into products (substances on the right hand side of the arrow) at the
same temperature and pressure, if the reaction is reversed (i.e., products are written on the left
hand side and reactants on the right hand side), then the numerical value of rH remains the
same, but its sign changes.
⚫ The utility of Hess’s law is considerable. In almost all the thermochemical numericals, Hess’s law
is used.
⚫ One of the important applications of Hess’s law is to determine enthalpy of reaction which is
difficult to determine experimentally. For example, the value rH for the reaction
1
C(graphite) + O2 (g) ⎯→ CO(g)
2
Which is difficult to determine experimentally, can be estimated from the following two reactions
for which rH can be determined experimentally.
C(graphite) + O2(g) ⎯→ CO2(g) rH1
1
CO(g) + O2(g) ⎯→ CO2(g) rH2
2
Substracting the latter from the former, we get
1
C(graphite) + O2(g) ⎯→ CO (g)
2
Consequently, rH = rH1 – rH2
APNI KAKSHA 4
4. Calculate heat of the following reaction at constant pressure,

F2O(g) + H2O(g) → O2 (g) + 2HF(g)
The heats of formation of F2O (g), H2O(g) and HF (g) are 5.5 kcal, –57kcal and –64 kcal
respectively.
Ans. – 76.5 kcal.
1
Sol. Given that (i) F2(g) + O2(g) → F2O(g); H = 5.5 kcal
2
1
(ii) H2(g) + O2(g) → H2O(g); H = – 57 kcal
2
1 1
(iii) H2(g) + F2(g) → HF(g); H = – 64 kcal
2 2
F2O and H2O in eqns. (i) and (ii) and in the eqn. given in the problem are on the opposite sides,
while HF in eqn. (iii) and in the eqn. given in the problem is on the same sides.
Thus applying, [2 × Eqn. (iii) – Eqn. (i) –Eqn. (ii)], we get
F2O (g) + H2O (g) → O2 (g) + 2HF(g)
H = – 5.5 – (– 57) + 2 × ( – 64) = – 76.5 kcal
5. If H2 + 1/2 O2 ⎯→ H2O, H = – 68 kcal

K + H2O + water ⎯→ KOH (aq) + 1/2 H2, H = – 48 kcal
KOH + water ⎯→ KOH (aq), H = – 14 kcal
Find the heat of formation of KOH.
Ans. –102 kcal.
Sol. If H2 + 1/2 O2 ⎯→ H2O, H = – 68 kcal
K + H2O + water ⎯→ KOH (aq) + 1/2 H2, H = – 48 kcal
KOH + water ⎯→ KOH (aq), H = – 14 kcal
fH KOH = (i) + (ii) – (iii) fH KOH = – 48 – 68 – (–14) = –102 kcal.
5.2 STANDARD ENTHALPY OF COMBUSTION :

⚫ It is the enthalpy change when one mole of a compound combines with the requisite amount of
oxygen to give products in their stable forms.
For example, the standard enthalpy of combustion of methane at 298 K is – 890 kJ mol–1. This
implies the following reaction :
CH4 (g) + 2O2(g) ⎯→ CO2(g) + 2H2O () H° = – 890 kJ mol–1
The standard enthalpy of combustion of methane at 298 K may be written as
Hc° (CH4, g, 298 K) = – 890 kJ mol–1
⚫ The data on the enthalpy of combustion can be determined experimentally.
⚫ With the help of such data, we can determine the enthalpy of formation of a compound, which
otherwise is difficult or impossible to determine experimentally. Consider for example, the
enthalpy of formation of CH4(g):
C(graphite) + 2H2(g) ⎯→ CH4(g)
APNI KAKSHA 5
First of all, the combination of carbon and hydrogen does not occur readily. Secondly, if the
reaction is even completed, the end product would not be pure methane. Therefore, the enthalpy
of formation of methane can be determined indirectly through the enthalpy of combustion of
methane :
CH4(g) + 2O2(g) ⎯→ CO2(g) + 2H2O()
HC°(CH4, g) = Hf°(CO2, g) + 2Hf°(H2O , ) – Hf° (CH4, g)
therefore Hf°(CH4, g) = Hf°(CO2, g) + 2Hf°(H2O , ) – HC° (CH4, g)
⚫ The enthalpies of formation of CO2 and H2O can be determined experimentally by the combustion
of carbon (graphite) and hydrogen. Thus, knowing the mesured value of HC°(CH4, g), the
enthalpy of formation of CH4 can be calculated. The value is
Hf°(CH4, g) = Hf°(CO2, g) + 2 Hf°(H2O , ) – HC° (CH4, g)
= [– 393 + 2 (–285) – (–890)] kJ mol–1 = – 73 kJ mol–1
or, equivalently, we may add the following three chemical equations.
C(graphite) + O2 (g) ⎯→ CO2 (g) CH° = – 393 kJ mol–1
2 [H2(g) + O2 (g) ⎯→ H2O()] rH° = 2(– 285) kJ mol–1
– [CH4(g) + 2O2 (g) ⎯→ CO2 (g) + 2H2O()] rH° = –(– 890) kJ mol–1
––––––––––––––––––––––––––––––––––––––– ––––––––––––––––––––––
C(graphite) + 2H2(g) ⎯→ CH4 (g) fH° = – 73 kJ mol–1
6. The standard enthalpy of formation of FeO & Fe2O3 is - 65 kcal mol-1 and -197 kcalmol-1
respectively. A mixture of two oxides contains FeO & Fe2O3 in the mole ratio 2 : 1. If by oxidation,
it is changed into a 1 : 2 mole ratio mixture, how much of heat will be released per mole of the
initial mixture ?
(A) 13.4 kcal/mole (B) 14.6 kcal/mole (C) 15.7 kcal/mole (D) 16.8 kcal/mole
Ans. (A)
Sol. FeO + Fe2O3
2x x
1
Fe + O2 ⎯→FeO = – 65 Kcal/mole
2
3
2Fe + O2 ⎯→Fe2O3 = – 197 Kcal/mole
2
1
2FeO + O2 ⎯→ Fe2O3
2
H = –197 + 65 × 2 H = – 67 Kcal/mole
1
2FeO + O2 ⎯→Fe2O3
2
2 1
3 3
APNI KAKSHA 6
2 1
– 2x +x
3 3
2
− 2x 1
3 1
= x =
1 5
+x 2
3
1
So, energy released = × 67 = 13.4 kcal/mole
5
5.1.2 MEASUREMENT OF ENTHALPY OF COMBUSTION :

Enthalpy of combustion are usually measured
by placing a known mass of the compound in a
closed steel container (known as bomb
calorimeter).
The calorimeter is surrounded by a known
mass of water. The entire apparatus is kept in
an insulated jacket to prevent heat entering
into or leaving from the container, as shown in
figure. The sample is ignited electrically to
bring about the combustion reaction. The heat
evolved is used in raising the temperature of
water and the calorimeter.
If total heat capacity of calorimeter and all of its contents = C, rise in temperature = T
then heat released = q = CT of this heat is because of mass m of substance then :
due to 1 mole, heat released =   q = UC°

M
m
(constant volume reaction).
Now, CH° can be calculated by using CH° = CU° + ng RT.
Where ng is the change in stoichiometric number of gaseous species in the balanced chemical
equation representing the combustion process.
7. A gas mixture of 4 litres of ethylene and methane on complete combustion at 25ºC produces
6 litres of CO2 . Find out the amount of heat evolved on burning one litre of the gas mixture. The
heats of combustion of ethylene and methane are – 1464 and –976 kJ mol-1 at 25ºC.
Ans. – 50 kJ.
Sol. + O2 → CO2 + H2O

x lit. (4 – x)lit. 6 lit.
(say)
or x moles (4 – x) moles 6 moles
Applying POAC for C atoms,
2 × x + 1 × ( 4 – x ) = 1 × 6 ; x = 2 lit.
Thus, the volume of C2H4 = 2 lit., and volume of CH2 = 2 lit.
APNI KAKSHA 7
volume of C2H4 in a 1 litre mixture = 2/4 = 0.5 lit.

and volume of CH4 in a 1 litre mixture = 1 –0.5 = 0.5 lit.
Now, thermochemical reactions for C2H4 and CH4 are
C2H4 + 3O2 → 2CO2 + 2H2O; H = – 1464 kJ
CH4 + 2O2 → CO2 + 2H2O; H = – 976 kJ
As H values given are at 25ºC, let us first calculate the volume occupied by one mole of
any gas at 25ºC (supposing pressure as 1atm)
298
Volume per mole at 25ºC = × 22.4 = 24.4 lit.
273
1464
Thus, heat evolved in the combustion of 0.5 lit. of C2H4 = – × 0.5 = – 30 kJ
24.4
976
and heat evolved in the combustion of 0.5 lit.of CH4 = × 0.5 = –20 kJ.
24.4
 total heat evolved in the combustion of 1 litre of the mixture = –30 + (– 20) = – 50 kJ.
8. Calculate the amount of heat evolved during the complete combustion of 100 ml of liquid
benzene from the following data. (in KJ/mole).
(i) 18 g of graphite on complete combustion evolve 585 KJ heat
(ii) 15540 KJ heat is required to dissociate all the molecules of 1 litre water into H2 and O2.
(iii) The heat of formation of liquid benzene is 48 kJ/mol
(iv) Density of C6H6 (l) = 0.87 g/ml
Ans. 36 kJ
585
Sol. (i) C(s) + O2(g) ⎯→ CO2(g) ;  f H º = – 390 KJ/mol ;  f H º = × 12
18
15540
(ii) H2(g) + O2(g) ⎯→ H2O (l) ;  f H º = – 280 KJ/mol ;  f H º =
55.5
15
(iii) C6H6(l) + O2(g) ⎯→ 6CO2 (g) + 3H2O (l) ;  f H º = –48
2
Hº = [6(–390) + 3 (–280)] – 48= –3228 KJ/ mol
Mass of benzene is = 0.87 x 100 = 87 g
Heat evolved from 87 g benzene = 3600 KJ.
Hence, q = 3600 kJ.
5.3 INTEGRAL ENTHALPY OF SOLUTION :

The integral enthalpy of solution at the given concentration is the enthalpy change when
one mole of the solute is dissolved in a definite quantity of solvent to produce a solution
of a desired concentration.
APNI KAKSHA 8
While recording integral enthalpies of solution it is a general practice to state the amount
of the solvent in which 1 mole of solute is dissolved ; Thus
HCl(g) + 10H2O() ⎯→ HCl (10H2O) H1 = –69.5 kJ mol–1
indicates that when 1 mole of hydrogen chloride gas is dissolved in 10 mol of water, there
is an evolution of 69.5 kJ of heat. Other values are
(i) HCl(g) + 25 H2O() ⎯→ HCl (25H2O) H2 = –72.3 kJ mol–1
(ii) HCl(g) + 40 H2O() ⎯→ HCl (40H2O) H3 = –73.0 kJ mol–1
(iii) HCl(g) + 200 H2O() ⎯→ HCl (200H2O) H4 = –74.2 kJ mol–1
(iv) HCl(g) + aq ⎯→ HCl (aq) H5 = –75.0 kJ mol–1
Whenever amount of solvent is not specified then take its amount to be very large just
like in equation no.
9. Calculate the free energy change when 1 mole of NaCl is dissolved in water at 25ºC. Lattice energy
of NaCl = 777.8 kJ mol–1 ; S for dissolution = 0.043 kJ mol–1 and hydration energy of NaCl = –
774.1 kJ mol–1.
Sol. Hdissolution = Lattice energy + Hydration energy
= 777.8 – 774.1 = 3.7 kJ mol–1
Now G = H – TS
= 3.7 – 298 × 0.043 = 3.7 – 12.814
G = –9.114 kJ mol–1
5.3.1 ENTHALPY OF HYDRATION :

Enthalpy of hydration is used in following two ways.
⚫ Enthalpy of hydration of anhydrous or partially hydrated salts :
Enthalpy of hydration of a given anhydrous or partially hydrated salt is the enthalpy change when
it combines with the requisite amount of water to form a new hydrated stable salt.
For example, the hydration of anhydrous cupric sulphate is represented by
CuSO4(s) + 5H2O() → CuSO4.5 H2O(s)
There is a almost invariably a liberation of heat in such reactions, i.e. the value of H is negative.
CuSO4(s) + 800 H2O() → CuSO4 (800 H2O) Hr° = – 68 kJ mol–1
CuSO4.5H2O(s) + 795 H2O() → CuSO4 (800 H2O) Hr° = + 10 kJ mol–1
by subtraction, we get
CuSO4(s) + 5H2O() → CuSO4.5 H2O(s) Hr° = – 78 kJ mol–1
5.3.2 ENTHALPY OF HYDRATION OF GASEOUS IONS :

Enthalpy of hydration of any gaseous ion is the enthalpy change when 1 mole of the gaseous ion
is hydrated in large amount of water to form aqeous ion.
By convention, the standard enthalpy of formation of H+(aq) is taken to be zero.
Enthalpy of hydration of Cl¯ gaseous ions will be represented by :
APNI KAKSHA 9
Cl¯(g) + aq. —→ Cl¯(aq) Hr° = Hf° (Cl–, aq)
5.1.3 ENTHALPY OF FORMATION OF IONS :

The enthalpy change when one mole of hydrated ions is obtained from element in its standard
state as. ½ Cl2 (g) + aq ⎯→ Cl– (aq) Hr° = Hf° (Cl–, aq)
By convention, the standard enthlpy of formation of H+(aq) is taken to be zero.
We have seen that H+ (aq) + OH–(aq) → H2O(l) rH° = – 57.1 kJ mol–1
For this reaction, Hr° = Hf° (H2O,l) – {Hf° (H+, aq) + Hf° (OH–,aq)}
Hence, at 25ºC, we get Hf° (H+, aq) + Hf° (OH– ,aq) = Hf° (H2O, l) – Hr°
so Hf° (OH– ,aq) = {– 286.1 – (– 57.1)} kJ mol–1 = – 229.00 kJ mol–1
⚫ With the enthalpies of formation of these two ions, the enthalpy of formation of any other ion
can be found from the enthalpies of formation and solution of its pure compound with H+ or OH¯.
for example, the enthalpy of formation of Na+ can be calculated from the enthalpy of formation
and enthalpy of infinite dilute solution of NaOH. The two values are :
⚫ The chemical equation for the formation of infinite dilute solution of NaOH(s) is
NaOH(s) +aq. ⎯→ Na+(aq) + OH¯(aq) aqH°(NaOH, s) = –44.50 kJ mol–1
Since there are equal amounts of water on both sides of the above equation, the two enthalpies
give no net effect and thus
H°sol(NaOH, s) = fH°(Na+, aq) + fH°(OH¯, aq) – fH°(NaOH, s)
or fH° (Na+, aq) = H°sol(NaOH, s) – fH°(OH°, aq) + fH°(NaOH, s)
= [–44.50 – (–229.99) + (–425.61)] kJ mol–1 = –240.12 kJ mol–1
⚫ Similarly, from NaCl(aq) or HCl(aq), the enthalpy of formation of Cl¯(aq) can be determined, and
so on. The changes in enthalpy of any ionic reaction can then be found from these ionic enthalpies
of formation and the usual enthalpies of formation of compounds.
10. Calculate the enthalpy change when one mole of HCl(g) is dissolved in a very large amount of
water at 25°C. The change in state is : HCl(g) + aq ⎯→ H+(aq) + Cl¯(aq)
Given : fH (HCl, g) = – 92 kJ mol–1 and fH° (Cl¯, aq) = – 167 kJ mol–1
Ans. – 75 kJ mol–1
Sol. For the reaction, HCl(g) + aq ⎯→ H+(aq) + Cl¯(aq)

we have H° = fH°(Cl¯,aq) – fH°(HCl, g)
H° = [–167 – (–92 )] kJ mol–1 = – 75 kJ mol–1
5.4 ENTHALPY OF NEUTRALIZATION :

The amount of heat released when one gram equivalent of an acid is neutralised by one gram
equivalent of a base.
or
The amount of heat released in formation of one mole of water when an acid is neutralised by a base.
or
Enthalpy of neutralization is defined as the enthalpy change when one mole of H+ in dilute
solution combines with one mole of OH¯ to give rise to undissociated water, i.e.
APNI KAKSHA 10
H+(aq) + OH¯(aq) —→ H2O() H= –57.1 kJ/mole = –13.7 kcal/mol

Remember :
⚫ For Strong Acid + Strong Base, heat of neutralisation is always equal to –13.7 kcal/mole
or –57.1 kJ/mole.
⚫ For any other combination of acid and base this heat is less than –13.7 kcal/mole
or –57.1 kJ/mole.
5.4.1 ENTHALPY OF IONIZATION :

Whenever a weak acid (or base) reacts with a strong base (or acid), the release of heat is less
than 57.1 kJ mol–1.
It is because of the fact that these acids or bases are not completely ionized in solution. Some of
the heat is consumed in ionizing there acids and bases this heat is known as enthalpy of
ionization. Examples are :
HCN + Na+ OH– → Na+ + CN– + H2O rH° = – 12 kJ mol–1
CH3COOH + Na+OH– → Na+ + CH3COO– + H2O rH° = – 49 kJ mol–1
The enthalpy of ionization can be calculated as follows. The neutralization of a weak acid, say
HCN, may be represented in two steps, namely,
Ionization HCN —→ H+ + CN¯ H°1 = x
Neutralization H + OH¯ —→ H2O
+ H°2 = – 57.1 kJ/mole
The complete reaction is obtained by adding the above two steps. Thus
HCN + OH¯ —→ H2O + CN¯ H° = – 45.1 kJ/mole
Obviously, H° = H°1 + H°2
H°1 = H° − H°2 = [–45.1 – (–57.1)] = 12 kJ/mole
⚫ Greater the enthalpy of ionization of any weak acid or weak base, weaker will be the acid or base.
11. Enthalpy of neutralization of HCl by NaOH is –57.1 kJ/mol and by NH4OH is –51.1 kJ/mol.
Calculate the enthalpy of dissociation of NH4OH.
Ans. 6.0 kJ/mol
Sol. Given that, H+(aq) + NH4OH(aq) —→ NH4+(aq) + H2O() H = –51.1 kJ/mole
We may consider neutralization in two steps.
(i) Ionization NH4OH(aq) —→ NH4+(aq) + OH¯(aq) H1 = ?
(ii) Neutralization H+(aq) + OH¯(aq) —→ H2O() H2 = – 57.1 kJ/mole
Thus, H = H1 + H2
Therefore, H1 = H – H2 = – 51.1 kJ/mol + 57.1 kJ mol–1 = 6.0 kJ/mol
12. The enthalpy of formation of H2O(l) is –285 kJ mol–1 and enthalpy of neutralization of a strong
acid and a strong base is –55 kJ mol–1. What is the enthalpy of formation of OH¯ ions ?
Ans. –230 kJ mol–1
Sol : Given that, H+(aq) + OH¯(aq) ⎯→ H2O() fH = –285 kJ mol–1
neutH = f H(H2O, ) – fH(OH¯, aq)
APNI KAKSHA 11
Hence fH (OH¯, aq) = fH(H2O, ) – neutH

= [–285 – (–55 )] kJ mol–1 = –230 kJ mol–1
13. 50.0 mL of 0.10 M HCl is mixed with 50.0 mL of 0.10 M NaOH. The solution's temperature rises
by 3.0ºC. Calculate the enthalpy of neutralization per mole of HCl. (Assuming density of sol. = 1
g/ml & specifice heat of water is 4.2 J/g-K) is
Ans. – 2.52 × 102 kJ/mole.
Sol. Assuming density of solution is 1g/cc
and specipic heat is 4.2 J/g-K
q = msT = 100 × 4.2 × 3
millimoles of acid nuetralized = 5
100x4.2x3
H = – = – 168 kJ/mole.
5x10-3
5.5 ENTHALPY OF TRANSITION :

Enthalpy of transition is the enthalpy change when one mole of one allotropic form changes to
another.
For example : C(graphite) → C(diamond) Htrs0 = 1.90 kJ mol–1
so if C(graphite) + O2(g) → CO2(g) HC0 = – 393.51 kJ mol-1
and C(diamond) + O2(g) → CO2(g) HC0 = – 395.41 kJ mol–1
Subtracting, we have, C(graphite) → C(diamond) Htrs0 = 1.90 kJ mol–1
5.6 ENTHALPY OF PRECIPITATION :

Enthalpy of precipitation is the enthalpy change when one mole of a precipitate is formed.
For example : BaCl2(aq.) + Na2SO4(aq) → BaSO4(s) + 2NaCl(aq) rH0=–24.27 kJ mol–1
14. Calculate H° for the reaction, Ag+(aq) + Cl¯(aq) ⎯→ AgCl(s) at 25°C.
Given fH°(Ag+, aq) = 105 kJ mol–1, fH°(Cl¯, aq)= –167kJ mol–1 and fH°(AgCl, s) = –127 kJ mol–1
Ans. –65 kJ mol–1
Sol. For the reaction Ag+(aq) + Cl¯(aq) ⎯→ AgCl(s)
we have H° = fH° (AgCl, s) – fH°(Ag+, aq) – fH°(Cl¯, aq)
= [–127 – 105 – (–167 )] kJ mol–1 = –65 kJ mol–1
APNI KAKSHA 12
DO YOURSELF - 1
1. Benzene burns according to the following equation at 300 K (R = 25/3 J mole–1K–1)

2C6H6(l) + 15 O2 (g) ⎯→12 CO2 (g) + 6H2O(l) Ho = – 6547.5 KJ
What is the Uo for the combustion of 1.5 mol of benzene
(A) –3271 kJ (B) –9813 kJ (C) –4905 kJ (D) –9810 kJ
2. When 1.0 g of oxalic acid (H2C2O4) is burned in a bomb calorimeter whose heat capacity is
8.75 kJ/K, the temperature increases by 0.312 K. The enthalpy of combustion of oxalic acid
at 27ºC is :
(A) –245.7 kJ/mol (B) –244.4 kJ/mol (C) –241.9 kJ/mol (D) 246.9 kJ/mol
3. The heat of combustion of ethyl alcohol is –300 kcal. If the heats of formation of CO2 (g)
and H2O(l) are –94.3 and –68.5 kcal respectively, calculate the heat of formation of ethyl
alcohol.
4. The standard enthalpy of decomposition of the yellow complex H3NSO2 Into NH3 and SO2
is + 40 kJ mol–1. Calculate the standard enthalpy of formation of H3NSO2. H0f(NH3) = –
46.17 kJ mol–1, H0f(SO2) = – 296.83
5. When 12.0 g of carbon (graphite) reacted with oxygen to form CO and CO2 at 250C and
constant pressure, 252 kJ of heat was released and no carbon remained. If H0f (CO, g) =
– 110.5 kJ mol–1 and H0f (CO2,g) = – 393.5 kJ mol–1, calculate the mass of oxygen consumed.
6. The standard enthalpy of neutralization of KOH with HCN and HCl in dilute solution is –
2480 cal.mol–1and –13.68 kcalmol–1 respectively. Find the enthalpy of dissociation of
HCN at the same temperature.
5.5 BOND ENTHALPIES :

The bond enthalpy is the average of enthalpies required to dissociate the said bond present in
different gaseous compounds into free atoms or radicals in the gaseous state. While bond
dissociation enthalpy is the enthalpy required to dissociate a given bond of some specific
compound, for example the enthalpy of dissociation of the O–H bond depends on the nature of
molecular species from which the H atom is being separated. For example, in the water molecule.
H2O(g) → H(g) + OH(g) rH° = 501.87 kJ mol–1
However, to break the O–H bond in the hydroxyl radical required a different quantity of heat :
OH(g) → O(g) + H(g) rH° = 423.38 kJ mol–1
The bond enthalpy, HH, is defined as the average of these two values, that is :
501.87mol−1 + 423.38kJmol −1
HOH = = 462.625 kJ mol–1
2
In the case of diatomic molecules, such as H2, the bond enthalpy and bond dissociation enthalpy
are identical because each refers to the reaction.
H2(g) → 2H(g) HH – H = rH° = 435.93 kJ mol–1
APNI KAKSHA 13
Thus, the bond enthalpy given for any particular pair of atoms is the average value of the
dissociation enthalpies of the bond for a number of molecules in which the pair of atoms appears.
 Estimation of Enthalpy of a reaction from bond Enthalpies :

Let the enthalpy change for the gaseous reaction
H H H H
C C + H – Cl → H C C H
(g)
H H H Cl
(g) (g)
be required from the bond enthalpy data. This may be calculated as follows :
 Enthalpy required to break reactants   Enthalpy required to form products 
H =  − 
 into gasesous atoms   from the gasesous atoms 
= [4HC–H + HC=C + HH–Cl]R + [–5HC–H – HC–C – HC–Cl]P
= (HC=C + HH–Cl) – (HC–H + HC–C + HC–Cl)
15. Using the bond enthalpy data given below, calculate the enthalpy change for the reaction C2H4(g)
+ H2(g) ⎯→ C2H6(g)
Data : Bond Bond enthalpy

C–C 336 kJ mol–1
C=C 606 kJ mol–1
C–H 410 kJ mol–1
H–H 431 kJ mol–1
Ans. – 119 kJ/mol.
Sol. Diagrammatically, we represent the given reaction as follows :
Hr = (4HC–H + HC=C + HH–H) – (6HC–H + HC–C)

= (4 × 410 + 606 + 431) – ( 6× 410 + 336)
= 2677 – 2796
= – 119 kJ/mol.
APNI KAKSHA 14
16. Using the bond enthalpy data given below, estimate the enthalpy of formation of gaseous
isoprene
CH 2 = C – CH = CH 2
|
CH 3
Data Bond enthalpy of C – H bond = 413.38 kJ mol–1

Bond enthalpy of C – C bond = 347.69 kJ mol–1
Bond enthalpy of C = C bond = 615.05 kJ mol–1
Enthalpy of sublimation of carbon (graphite) = 718.39 kJ mol–1
Enthalpy of dissociation of H2(g) = 435.97 kJ mol–1
Ans. fH = 103.31 kJ mol–1
Sol. For isoprene, we have to form
2C – C bonds ; 2C = C bonds and 8C – H bonds
Method-1 For which energy released is

[2(+347.69) + 2(+615.05) + 8(+413.38)] kJ mol–1 = 5 232.52 kJ mol–1
that is, H (from gaseous atoms) = + 5232.52 kJ mol–1
The reaction corresponding to this is
5C(g) + 8H(g) → C5H8(g) fH1 = – 5232.52 kJ mol–1
But we want fH corresponding to the following equation

5C(graphite) + 4H2(g) → C5H8(g) fH = ?
This can be obtained by the following manipulations :

5C(g) + 8H(g) → C5H8(g) rH2 = – 5232.52 kJ mol–1
5C(graphite) → 5C(g) rH3 = 5 × 718.39 kJ mol–1
4H2(g) → 8H(g) rH4 = 4 × 435.97 kJ mol–1
Adding, we get
5C(graphite) + 4H2(g) → C5H8(g) fH = 103.31 kJ mol–1
Method-2 Diagrammatically, the above calculations may be represented as follows.
Applying Hess’s law, we get

fH = 5H3 + 4H4 – 2HC = C – 2HC – C – 8HC – H
APNI KAKSHA 15
= (5 x 718.39 + 4 x 435.97 – 2 x 615.05 – 2 x 347.69 – 8 x 413.38) kJ mol–1

fH = 103.31 kJ mol–1
5.7 Resonance Energy :

Difference between energy of resonance hybrid and resonating structure in which resonance
hybrid have lower energy because stabilised by resonance.
H°resonance = H°f, experimental – H°f, calclulated
= H°combustion, calclulated – H°combustion, experimental
17. Calculate the heat of formation of benzene from the following data, assuming no resonance.
Bond energies :
C – C = 83 kcal, C = C = 140 kcal, C – H = 99 kcal
Heat of atomisation of C = 170 .9 kcal
Heat of atomisation of H = 52.1 kcal
Sol. We have to calculate H for the reaction
6C (s) + 3H2(g) → C6 H6 (g)
For reactants :
Heat of atomisation of 6 moles of C = 6 ×170.9 kcal
heat of atomisation of 6 moles of H = 6 × 52.1 kcal
For products :
Heat of formation of 6 moles of C – H bonds = – 6 × 99
Heat of formation of 3 moles of C–C = – 3 × 83
Heat of formation of 3 moles of C = C bonds = –3 × 140
on adding, we get heat of formation of C6H6,i.e.,
fH = 6 ×170.9 + 6 × 52.1– 6 × 99 – 3 × 83 –3 × 140 = –75 kcal
DO YOURSELF - 2
1. Calculate the bond energy of Cl–Cl bond from the following data :
CH4(g) + Cl2(g) ⎯⎯ → CH3Cl(g) + HCl(g); H = – 100.3 kJ. Also the bond enthalpies of
C–H, C–Cl, H–Cl bonds are 413, 326 and 431 kJ mol–1 respectively.
2. Calculate Hºr for the reaction CH2Cl2 (g) ⎯⎯

→ C(g) + 2H(g) + 2Cl(g). The average bond
enthalpies of C–H and C–Cl bonds are 414 kJ mol–1 and 330 kJ mol–1.
3. Calculate the enthalpy change (H) of the following reaction
APNI KAKSHA 16
2C2H2(g) + 5O2(g) ⎯⎯ → 4CO2(g) + 2H2O(g) given average bond enthalpies of various

bonds, i.e., C–H, C  C, O = O, C = O, O–H as 414, 814, 499, 724 and 640 kJ mol–1 respectively.
4. Estimate the average S–F bond enthalpy in SF6. The values of standard enthalpy of
formation of SF6(g), S(g) and F(g) are : – 1100, 274 and 80 kJ mol–1 respectively.
5. NH3(g) + 3Cl2(g) ⎯⎯
→ NCl3(g) + 3HCl(g) ; H 1
N2(g) + 3H2(g) ⎯⎯
→ 2NH3(g) ; H 2
H2(g) + Cl2(g) ⎯⎯ → 2HCl(g) ; H 3
The heat of formation of NCl3(g) in the terms of H1, H2 and H3 is
H 2 3 H 2 3
(A) H f = −H1 + − H 3 (B) H f = H1 + − H 3
2 2 2 2
H 2 3
(C) H f = H1 − − H 3 (D) None
2 2
6. Ethanol can undergoes decomposition to form two sets of products.
If the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of product gases, then the energy
involved in the decomposition of 1 mole of ethanol is
(A) 65.98kJ (B) 48.137 kJ (C) 48.46 kJ (D) 57.22 kJ
7. Find the bond enthalpy of S – S bond from the following data :

C2H5 – S – C2H5(g) fH° = – 147 kJ mol–1
C2H5 – S – S – C2H5(g) fH° = –201 kJ mol–1
S(g) fH° = 222 kJ mol–1
ANSWER KEY
DO YOURSELF - 1
1. (C)
Sol. From given reaction Dng = 12 – 15 = – 3
so U° = H° – ng RT = – 6542 + 3RT
for 1.5 mole, U° = { –6542 + 3RT} = 6534.5 kJ
2. (C)
Sol. H2C2O4(l) + O2(g) ⎯→ H2O(l) + 2CO2(g);
ng = 3/2
Uc = –8.75×0.312 × 90 = – 245.7 kJ/mol
APNI KAKSHA 17
1.5  8.314  300

= – 245.7 + = – 241.947 kJ/mol.
1000
3. (–94.1 kcal)
Sol. C2H6O + 3O2(g) ⎯⎯ → 2CO2 + 3H2O. H = – 300 kcal
Hcomb = 2Hf ,CO + 3Hf ,H O – Hf ,C H O = 2(–94.3) + 3(–68.5) + 300 = –94.1 Kcal
2 2 2 6
4. – 383 kJ mol–1
Sol. NH3(g) + SO2(g) ⎯⎯ → NH3SO2(s) H0 = – 40 kJ mol–1
H0 = H0f (NH3SO2,S) – H0f(NH3,g) – H0f (SO2,g)
Solving for H0f (NH3SO2,S)
H0f = (NH3SO2,S) – H0f (NH3,g) + H0f (SO2,g) + H0
= (– 46.17 – 296.83 – 40) KJ mol–1 = – 383 kJ mol–1
5. 24 g
Sol. We have
12.0g
Amount of carbon = = 1 mol
12.0 g mol−1
The equations to be considered are
C(graphite) + ½O2(g) ⎯⎯
→ CO(g) H0 = – 110.5 kJ mol–1
C(graphite) + O2(g) ⎯⎯ → CO2(g) H0 = – 393.5 kJ mol–1
Let the amount x of carbon be converted into CO and the remaining (i.e. 1.0 mol – x) into CO2. we
will have [x (– 110.5) + (1.0 mol – x) (– 393.5)] kJ mol–1 = – 313.8 kJ
Which gives x = mol = 0.5 mol
 0.5
Amount of oxygen needed =  + (1.0 − 0.5 )  mol = 0.75 mol
 2 
Mass of oxygen needed = (0.75 mol) (32 g mol–1) = 24 g
6. 11.2 Kcal
Sol. Hdissociation(WA) = –Hneut(SA + SB) + Hneut(WA + SB)
Hdiss(HCN) = +13.68 – 2.48 = 11.2 Kcal
DO YOURSELF - 2
1. 243.7 kJ mol–1
Sol. H = 4HC−H + HCl−Cl − 3HC−H − HC−Cl −HH−Cl
= – 100.3 = (4 × 413) + x – (3 × 413) – 326 – 431
x = 243.7 KJ mol–1
2. 1488 kJ mol–1.
Sol.
Hr = 2HC–H + 2HC–Cl = 2 × 414 + 2 × 330 = 828 + 660 = 1488 kJ/mol.
APNI KAKSHA 18
3. – 2573 kJ/mole
Sol.
Hr = 2[HC  C+ 2HC–H ] + 5 HO = O – 4 [2HC = O] –2 [2HO–H ]

Hr = 2 [814 + 2 × 414 ] + 5 [499] – [8 × 724] – 4 [640] = 3284 + 2495 – 5792 – 2560 = – 2573
kJ/mole.
4. 309 kJ mol–1
Sol. To calculate the average S–F bond enthalpy, we determine the enthalpy change for the following
reaction.
S(g) + 6F(g) ⎯⎯ → SF6(g)
H0f 275 kJ mol–1 80 kJ mol–1 1100 kJ mol–1
H0f = Hf0 (SF6,g) – [Hf0(S,g) + 6H0f (F, g)]
= [–1100 – (274 + 6 × 80)] kJ mol–1
-ΔH 0f (SF6 , g ) 1854 kJ mol-1
Hence H(S–F) = = = 309 kJ mol–1
6 6
5. (B)
1 3
Sol. N2(g) + Cl2(g) NCl3(g)
2 2
H 2 3
H = H 1 + – H 3
2 2
6. (B)
8 1
Sol. r H = × 45.54 + × 68.91 = 48.137 kJ.
9 9
7. Given that
(i) 4C(s) + 5H2(g) + S(s) ⎯→ C2H5 – S – C2H5(g) fH° = –147 kJ mol–1
(ii) 4C(s) + 5H2(g) + 2S(s) ⎯→ C2H5 – S – S – C2H5(g) fH° = –201 kJ mol–1
Subtracting Eq. (i) from Eq. (ii), we get
C2H5 – S – C2H5(g) + S(s) ⎯→ C2H5 – S – S – C2H5(g) rH° = –54 kJ mol–1
Adding to this, the following equation
S(g) ⎯→ S(s) fH° = –222 kJ mol–1
We get
C2H5 – S – C2H5(g) + S(g) ⎯→ C2H5 – S – S – C2H5(g) rH° = –276 kJ mol–1
In the last equation 276 kJ of heat evolved because of the S–S bond formation.
Hence, the bond enthalpy of S – S is 276 kJ mol–1.
APNI KAKSHA 19
EXERCISE # O-I
ENTHALPY OF FORMATION
1. Which of the following equations represents a reaction that provides the heat of formation of
CH3Cl?
(A) C(s) + HCl(g) + H2(g) → CH3Cl(g) (B) C(s) + 3/2 H2(g) + 1/2 Cl2(g) → CH3Cl(g)
(C) C(s) + 3H(g) + Cl(g) → CH3Cl(g) (D) CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g)
2. Use the given standard enthalpies of formation to determine the heat of reaction of the
following reaction:
TiCl4(g) + 2 H2O(g) → TiO2(g) + 4 HCl(g)
H°f TiCl4(g) = –763.2 kJ/mole H°f TiO2(g) = –944.7 kJ/mole
H°f H2O(g) = –241.8 kJ/mole H°f HCl(g) = –92.3 kJ/mole
(A) –278.1 kJ (B) +369.2 kJ (C) +67.1 kJ (D) –67.1 kJ
3. Using the following information calculate the heat of formation of CH4.

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ; rH° = – 890.4 kJ
H°f CO2(g) = – 393.5 kJ/mole H°f H2O(l) = – 285.9 kJ/mole
(A) – 98.6 kJ (B) – 65.5 kJ (C) – 74.9 kJ (D) – 43.5 kJ
4. The standard enthalpy of formation of ammonia gas is -

Given : N2H4(g) + H2(g) ⎯→ 2NH3 (g) ; H r = – 40kJ /mol
H f [N2H4(g)] = – 120kJ /mol
(A) –60 kJ (B) –180 kJ (C) 40 kJ (D) –80 kJ
5. The heats of formation of CO2(g) and H2O(l) are –394 kJ/mole and –285.8 kJ/mole respectively
Using the data for the following reaction, calculate the heat of formation of C2H2(g).
2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(l) ; rH° = – 2601 kJ
(A) – 238.6 kJ (B) 253.2 kJ (C) 238.7 kJ (D) 226.7 kJ
6. NH3(g) + 3Cl2(g) → NCl3(g) + 3HCl (g); –H1

N2(g) + 3H2(g) → 2NH3(g); H2
H2(g) + Cl2(g) → 2HCl (g) ; H3
The enthalpy of formation of NCl3 (g) in the terms of H1, H2 and H3 is
H 2 3 H 2 3
(A) Hf = – H1 + − H 3 (B) Hf = H1 + − H 3
2 2 2 2
APNI KAKSHA 20
H 2 3 H 2 3
(C) Hf = H1 − − H 3 (D) Hf = H1 + + H 3
2 2 2 2
7. Study the following thermochemical equations :

A→B; ; H = +100kcal
B→C ; H = – 80kcal
The correct order of enthalpies of formation of A, B and C is -
(A) A < B < C (B) A < C < B (C) C < A < B (D) B < C < A
ENTHALPY OF COMBUSTION
8. The heats of formation of CO2(g) and H2O(l) are –394 kJ/mole and –285.8 kJ/mole respectively
& H Combustion [C3H8(g)] = –2221.6 kJ. Then calculate the heat of formation of C3H8(g).
(A) 212.2 kJ (B) – 143.3 kJ (C) 185.4 kJ (D) – 103.6 kJ
9. What amount of heat energy (kJ) is released in the combustion of 12.0 g of C3H4?
(Atomic weights: C = 12, H = 1, O = 16).
C3H4(g) + 4O2(g) → 3CO2(g) + 2H2O(l)
H° = –1939.1 kJ
(A) 725 (B) 504 (C) 783 (D) 581.73
10. What is the ratio of the enthalpy change on combustion of hydrogen atoms to steam to the
enthalpy change on combustion of an equal mass of hydrogen molecules to steam?
1
Given : H2(g) + O2(g) ⎯→ H2O(g) ; H = – 242 kJ
2
B.E. (H – H) = 436 kJ
(A) 0.80 : 1 (B) 1 : 0.80 (C) 1.80 : 1 (D) 2.80 : 1
11. Hydrazine, a component of rocket fuel, undergoes combustion to yield N2 and H2O.
N2H4(l) + O2 (g) ⎯→ N2 (g) + 2H2O (l)
What is the enthalpy change of combustion of N2H4 (kJ/mole)
Given Reaction H/kJ
2NH3 (g) + 3N2O (g) ⎯→ 4N2(g) + 3H2O (l) – 1011 kJ
N2O (g) + 3H2 (g) ⎯→ N2H4 (l) + H2O (l) – 317 kJ
4NH3 (g) + O2 (g) ⎯→ 2N2H4 (l) + 2H2O (l) – 286 kJ
APNI KAKSHA 21
1
H2 (g) + O2 (g) ⎯→ H2O (l) – 285 kJ
2
(A) – 620.5 (B) – 622.75 (C) 1167.5 (D) + 622.75
ENTHALPY OF REACTION AND RELATION BETWEEN H AND U
12. Find rU° for the reaction 4HCl (g) + O2 (g) 2Cl2(g) + 2H2O (g) at 300 K. Assume all gases
are ideal.

Given: H2(g) + Cl2(g) ⎯→ 2HCl (g)  r H 300 = –184.5 kJ/mole

2H2(g) + O2(g) ⎯→ 2H2O (g)  r H 300 = –483 kJ/mole (Use R=8.3 J/mole)
(A) 111.5 kJ/mole (B) –109.01 kJ/mole (C) –111.5 kJ/mole (D) None
13. The enthalpy changes of the following reactions at 27°C are

1
Na(s) + Cl2 (g) ⎯→ NaCl (s) rH = –411 kJ/mol
2
H2(g) + S (s) + 2O2 (g) ⎯→ H2SO4 (l) rH = –811 kJ/mol
2Na(s) + S(s) + 2O2 (g) ⎯→ Na2SO4 (s) rH = –1382 kJ/mol
1 1
H2(g) + Cl2(g) ⎯→ HCl (g) rH = –92 kJ/mol;
2 2
from these data, the heat change of reaction at constant volume (in kJ/mol) at 27°C for the
process (R = 8.3 J/K-mol)
2NaCl (s) + H2SO4 (l) ⎯→ Na2SO4 (s) + 2HCl (g) is
(A) 67 (B) 62.02 (C) 71.98 (D) 50
14. 2NO2(g) → N2O4(g)

U°f [N2O4(g)] = 2kcal/ mole
and U°reaction = –16 kcal /mol then calculate H°formation of NO2 at 727ºC
(A) 9 kcal /mol (B) 4.5 kcal /mol (C) 8 kcal /mol (D) 10 kcal /mol
BOND ENTHALPY , ENTHALPY OF ATOMISATION, ENTHALPY OF VAPOURISATION

15. The bond dissociation energy of gaseous H2, Cl2 and HCl are 104, 58 and 103 kcal mol–1
respectively. The enthalpy of formation for HCl gas will be :-
(A) –44.0 kcal (B) –22.0 kcal (C) 22.0 kcal (D) 44.0 kcal
APNI KAKSHA 22
16. The enthalpy change for the following reaction is 513kJ. Calculate the average Cl – F bond
energy.
ClF3(g) → Cl(g) + 3 F(g)
(A) 1542 kJ (B) 88 kJ (C) 171 kJ (D) 514 kJ
17. The reaction CH4(g) + Cl2(g) ⎯→ CH3Cl(g) + HCl(g) has H = –25 kcal.
Bond Bond Enthalpy kcal

C–Cl 84
H–Cl 103
C–H X
Cl–Cl Y
x:y=9:5
From the given data, what is the bond enthalpy of Cl—Cl bond
(A) 70 kcal (B) 80 kcal (C) 67.75 kcal (D) 57.75 kcal
18. If x1, x2 and x3 are enthalpies of H–H, O=O and O–H bonds respectively, and x4 is the enthalpy of
vaporisation of water, estimate the standard enthalpy of combustion of H2(g)
x2 x2
(A) x1 + − 2x 3 + x 4 (B) x1 + − 2x 3 − x 4
2 2
x2 x2
(C) x1 + − x 3 + x4 (D) 2x 3 − x1 − − x4
2 2
19. The enthalpy change at 298K for decomposition is given in following steps-
Step-1: H2O(g) → H(g) + OH(g)H = 498kJ/mol–1
Step-2: OH(g) → H(g) + O(g)H = 428kJ/mol–1
Then value of mean bond enthalpy of O–H bond will be -
(A) 498 kJ/mol (B) 463kJ/mol (C) 428 kJ/mol (D) 70 kJ/mol
20. If bond enthalpy of C–C and C = C are 348 kJ /mole and 615 kJ/mole respectively then calculate
enthalpy change (in kJ/mole) which occurs during the isomerisation of cyclopropane (g) into
propene (g)
(A) 19 (B) 81 (C) 1 (D) 20
APNI KAKSHA 23
HYDRATION ENTHALPY, ENTHALPY OF SOLUTION, HYDRATION AND DILUTION

21. The lattice enthalpy of solid NaCl is 772 kJmol–1 and enthalpy of solution is 2 kJmol–1.
If the hydration enthalpy of Na+(g) & Cl–(g) ions are in the ratio of 3:2.5, what is the enthalpy of
hydration of chloride ion?
(A) –140 kJmol–1 (B) –350 kJmol–1 (C) –351.81 kJmol–1 (D) None
22. Enthalpy of dilution of 4M HCl to 2M HCl is –2.5 kJ/mol. Find enthalpy change when 500 ml of
HCl is diluted from 4M to 2M
(A) –2.5 kJ/mol (B) –5 kJ/mol (C) –10 kJ/mol (D) –1.25 kJ/mol
RESONANCE ENERGY & ENTHALPY OF NEUTRALISATION

23. If enthalpy change for hydrogenation of ethylene is –132 kJ/mole and enthalpy of formation
1,3-butadiene (g) and butane (g) are 115 kJ and –140 kJ/mole respectively then calculate
resonance energy of 1,3-budadiene (in kJ).
(A) 9 kJ (B) 18 kJ (C) 4 kJ (D) 10 kJ
24. Magnitude of enthalpy of neutralization is minimum for :

(A) HCN + KOH (B) HCl + KOH (C) HCl + NH4OH (D) HCN + NH4OH
25. Enthalpy of neutralization of NaOH with H2SO4 is –57.3 KJ eq–1 and ethanoic acid –55.2 KJ eq–1.
which of the following is the best explanation of this difference -
(A) Ethanoic acid is a weak acid and thus requires less NaOH for neutralization
(B) Ethanoic acid is only partly ionised, neutralization is therefore incomplete
(C) Ethanoic acid is monobasic while H2SO4 is dibasic
(D) Some heat is used to ionize ethanoic acid completely
26. 0.2 M ; 100 ml NaOH is mixed with 0.4 M ; 100 ml HCl solution. Determine energy released
during the reaction.
Given : H+(aq) + OH–(aq) ⎯⎯→ H2O(l) ;
H = –57.5 KJ mol–1
(A) 1150 J (B) 1150 KJ (C) 2300 J (D) 2300 KJ
APNI KAKSHA 24
27. Enthalpy of neutralization of H2C2O4 acid is –109 kJ/mol using NaOH. If enthalpy of
neutralization of HCl by NaOH is –57 kJ/mol. Calculate Hionization of H2C2O4 into its ions
(A) 50.84 kJ/mol (B) 5 kJ/mol (C) 2.5 kJ/mol (D) 10 kJ/mol
28. H 0f of water is –285.8 kJ mol–1. If enthalpy of neutralisation of monoacid strong base is
–57.3 kJ mol–1, H 0f of OH– ion will be
(A) –228.5 kJ mol–1 (B) 228.5 kJ mol–1 (C) 114.25 kJ mol–1 (D) –114.25 kJ mol–1
KIRCHOFF EQUATION & SOME MIXED QUESTIONS

29. The molar heat capacities at constant pressure (assume constant with respect to temperature)
of A, B and C are in ratio of 1.5 : 3.0 : 2.0. If enthalpy change for the exothermic reaction
A + 2B ⎯→ 3C at 300 K is – 10 kJ/mol & Cp,m (B) is 300 J/mol then enthalpy change at 310 K is:
(A) – 8.5 kJ/mol (B) 8.5 kJ/mol (C) – 11.5 kJ/mol (D) none of these
30. Ethanol can undergoes decomposition to form two sets of products
if the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of product gases, then the enthalpy involved
in the decomposition of 1 mole of ethanol is
(A) 65.98 kJ (B) 48.137 kJ (C) 48.46 kJ (D) 57.22 kJ
31. Reactions involving gold have been of particular interest to a chemist . Consider the following
reactions,
Au(OH)3 + 4 HCl ⎯→ HAuCl4 + 3 H2O, H = 28 kCal
Au(OH)3 + 4 HBr ⎯→ HAuBr4 + 3 H2O , H = –36.8 kCal
In an experiment there was an absorption of 0.44 kCal when one mole of HAuBr4 was mixed
with 4 moles of HCl . What is the percentage conversion of HAuBr4 into HAuCl4 ?
(A) 0.5 % (B) 0.6 % (C) 5 % (D) 50 %
32. PCl5(g) PCl3(g) + Cl2(g)
G°f [PCl5(g)] = – 74 kcal /mol G°f [PCl3(g)] = – 60 kcal /mol

then calculate value of equilibrium constant for dissociation of PCl5(g) at 727ºC temperature ?
APNI KAKSHA 25
(ln2 = 0.7)
(A) 210 (B) 2–10 (C) 2–20 (D) 2+20
33. For the allotropic change represented by the equation C (graphite) → C (diamond), H= 1.9 kJ.
If 6 g of diamond and 6 g of graphite are separately burnt to yield CO2, the enthalpy liberated in
first case is
(A) less than in the second case by 1.9 kJ (B) more than in the second case by 11.4 kJ
(C) more than in the second case by 0.95 kJ (D) less than in the second case by 11.4 Kj
APNI KAKSHA 26
EXERCISE # S-I
ENTHALPY OF FORMATION AND COMBUSTION
1. From the following data at 25°C, Calculate the standard enthalpy of formation of FeO(s) and of
Fe2O3(s).
Reaction rH° (kJ/mole)
(A) Fe2O3(s) + 3C(graphite) → 2Fe (s) + 3CO(g) 492
(B) FeO (s) + C(graphite) → Fe(s) + CO(g) 155
(C) C(graphite) + O2(g) → CO2(g) –393
(D) CO(g) +1/2 O2(g) → CO2(g) –282
2. When 2 moles of C2H6(g) are completely burnt 3120 kJ of heat is liberated. Calculate the
enthalpy of formation, of C2H6(g) . Given fH for CO2(g) & H2O (l) are – 395 & – 286 kJ
respectively.
3. Calculate standard enthalpies of formation of carbon–di–sulphide (l). Given the standard

enthalpy of combustion of carbon (s), sulphur (s) and carbon–di–sulphide (l) are : – 393, – 293
and – 1108 kJ mol–1 respectively.
4. The enthalpy changes for the reaction C3H8(g) + H2(g) ⎯→ C2H6(g) + CH4(g) at 25º C is – 55.7
kJ/mol. Calculate the enthalpy of combustion of C2H6(g). The enthalpy of combustion of H2, &
CH4 and propane are –285.8, –890.0 kJ/mol and –2220 kJ mol–1 respectively.
5. A cylinder of gas is assumed to contains 11.2 kg of butane. If a normal family needs 20,000 kJ of
energy per day for cooking, how long will the cylinder last if the enthalpy of combustion,
H = – 2658 kJ/mole for butane.
ENTHALPY OF REACTION AND RELATION BETWEEN H AND U

6. At 300 K, the standard enthalpies of formation of C6H5COOH(s), CO2(g) & H2O (l) are;
– 408, –393 & –286 kJ mol–1 respectively.
Calculate the heat of combustion of benzoic acid at:
(i) constant pressure
(ii) constant volume.
APNI KAKSHA 27
BOMB CALORIMETER, BOND ENTHALPY , ENTHALPY OF ATOMISATION, ENTHALPY OF

VAPOURISATION
7. 0.16 g of methane was subjected to combustion at 27ºC in a bomb Calorimeter.
The temperature of Calorimeter system (including water) was found to rise by 0.5ºC. Calculate
the heat of combustion of methane at
(i) constant volume (ii) constant pressure.
The thermal capacity of Calorimeter system is 17.7 kJ K–1. (R = 8.313 mol–1 K–1)
8. 1.00 L sample of a mixture of CH4(g) & O2(g) measured at 27ºC & 760 torr was allowed to react
at constant pressure in a Calorimeter which together with its contents had a heat capacity of
1200 Cal/K. The complete combustion of methane to CO2 & H2O caused a temperature rise, in
the Calorimeter, of 0.25K. What was the mole percent of CH4 in the original mixture?
Hºcomb (CH4) = –200 k Cal mol–1.
9. XeF2 (g) + H2(g) ⎯→ 2HF(g) + Xe(g) H° = – 430 kJ

using the following bond energies: H–H = 435 kJ/mol
H–F = 565 kJ/mol
Calculate the average bond energy of Xe-F in XeF2.
10. For the reaction

N2H4(g) → N2H2(g) + H2(g) rH° = 109 kJ /mol
Calculate the bond enthalpy of N = N.
Given: B.E.(N–N) = 163kJ/mol, B.E.(N–H) = 391 kJ/mol, B.E. (H–H) = 436 kJ/mol
11. Using the bond enthalpy data given below, calculate the enthalpy change for the reaction.
C2H4(g) + H2(g) → C2H6(g)
Data:
Bond C–C C=C C–H H–H
Bond Enthalpy 336 kJ/mol 606 kJ/mol 410 kJ/mol 431 kJ/mol
APNI KAKSHA 28
12. Using bond enthalpy data, calculate enthalpy of formation of isoprene.
Given : C — H = 98.8 k Cal ; H — H = 104 k Cal ;

C — C = 83 k Cal ; C — C = 147 k Cal &
C(s) → C(g) = 171 k Cal.
13. Compute the enthalpy of formation of liquid methyl alcohol in kJ mol–1, using the following
data.
Enthalpy of vaporisation of liquid CH3OH = 38 kJ/ mol.
Enthalpy of formation of gaseous atoms from the elements in their standard states are
H → 218 kJ / mol ; C → 715 kJ / mol ; O → 249 kJ / mol.
Bond Enthalpies
C – H → 415 kJ /mol ; C – O → 356 kJ / mol ; O – H → 463 kJ / mol
14. The enthalpy of atomization of PH3 is 954 kJ mol–1 and that of P2H4 is 1485 kJ mol–1.
What is the bond enthalpy of the P–P bond?
15. Find the enthalpy of S–S bond from the following data.
(i) C2H5 – S – C2H5 (g) fH° = – 150 kJ/mol
(ii) C2H5 – S – S – C2H5 (g) fH° = – 200 kJ/mol
(iii) S (g) fH° = 225 kJ/mol
16. The polymerisation of ethylene to linear polyethylene is represented by the reaction

n CH2 = CH2 → (–CH2 – CH2)n
where n has a large integral value. Given that the average enthalpies of bond dissociation for
C=C & C–C at 298 K are + 590 & + 331 kJ mol–1 respectively. Calculate the enthalpy of
polymerisation per mole of ethylene at 298 K.
BORN HABER CYCLE AND LATTICE ENTHALPY

17. Calculate the enthalpy change for the reaction XeF4 ⎯→ Xe+ + F– + F2 + F.
The average Xe–F bond enthalpy is 34 kcal/mol, first I.E. of Xe is 279 kcal/mol, electron affinity
of F is 85 kcal/mol & bond dissociation enthalpy of F2 is 38 kcal/mol.
APNI KAKSHA 29
18. Calculate the electron gain enthalpy of fluorine atom using the following data. Make Born –
Haber's cycle. All the values are in kJ mol–1 at 25º C . Hdiss (F2) = 160, fH (NaF(s)) = –571, I.E.
[Na(g)] = 494, Hvap [Na(s)] = 101, Lattice enthalpy of NaF(s) = 894.
19. The Born–Haber cycle for formation of rubidium chloride (RbCl) is given below
(the enthalpies are in k Cal mol–1)
Find the value of X.
20. By using the following data draw an appropriate enthalpy cycle & calculate the enthalpy change
of hydration of (i) the chloride ion ; (ii) the iodide ion.
Comment on the difference in their values.
enthalpy change of solution of NaCl(s) = –2 kJ/mol.
enthalpy change of solution of NaI(s) = +2 kJ/mol.
enthalpy change of hydration of Na+(g) = –390 kJ/mol.
lattice enthalpy of NaCl = 772 kJ/mol.
lattice enthalpy of NaI = 699 kJ/mol.
HYDRATION ENTHALPY, ENTHALPY OF SOLUTION , HYDRATION AND DILUTION.

OTHER TYPES OF ENTHALPIES OF REACTION
21. The enthalpy of solution of anhydrous CuSO4(s) is –16 kCal and that of CuSO4.5H2O is 3 kCal.
Calculate the enthalpy of hydration of CuSO4(s).
22. If the enthalpy of formation of HCl(g) and Cl–(aq) are –90 kJ/mole and –170 kJ/mol, find the
enthalpy of solution of hydrogen chloride gas.
RESONANCE ENERGY
23. Calculate resonance enthalpy of CO2(g) from following data
H 0combustion [C(graphite)] = – 390 kJ/mol
H 0atomisation [C(graphite)] = 715 kJ/mol
APNI KAKSHA 30
H 0B.E. [O = O] = 500 kJ/mol
H 0B.E. [C = O] = 675 kJ/mol
24. Use the following data to answer the questions below :
Calculate the resonance energy of anthracene,
25. Calculate enthalpy of combustion of propane [C3H8 (g)] in kJ/mol at 298 K.

Given : B.E. (O = O) = 498 kJ/mole ; B.E. (C = O) = 804 kJ/mole
B.E. (C–H) = 410 kJ/mole ; B.E. (O–H) = 464 kJ/mole
B.E. (C–C) = 345 kJ/mole ; Resonance energy of
CO2 (g) = – 143 kJ/mole
Hvaporization (H2O, l) = 41 kJ/mole
ENTHALPY OF NEUTRALISATION
26. The enthalpies of neutralization of NaOH & NH4OH by HCl are –13680 Cal and –12270 Cal
respectively. What would be the enthalpy change if one gram equivalent of NaOH is added to
one gram equivalent of NH4Cl in solution ? Assume that NH4OH and NaCl are quantitatively
obtained.
27. H+ + OH– ⎯→ H2O ; Hº = –57 kJ/mol

Hionisation
0
[HCN] = 45 kJ/mol
If 200 ml , 1/10 M Ba(OH)2 solution is mixed with 500 ml , 1/10M HCN, then find out the heat
evolved.
28. Two solutions initially at 25°C were mixed in an adiabatic constant pressure Calorimeter. One
contains 400 ml of 0.2 M weak monoprotic acid solution. The other contain 100 ml of 0.80 M
NaOH. After mixing temperature increased to 26.2 °C. How much heat is evolved in the
neutralization of 1 mole of acid? Assume density of solution 1.0 g/cm3, and specific heat of
solution 4.2 J/g-K. Neglect heat capacity of the Calorimeter.
APNI KAKSHA 31
29. Calculate the enthalpy change when infinitely dilute solution of CaCl2 and Na2CO3 are mixed
fH° for Ca2+(aq), CO32– (aq) and CaCO3 (s) are – 129, – 161, – 288 kcal mol–1 respectively.
KIRCHOFF EQUATION
30. Determine H for the following reaction at 500K and constant pressure :
CO(g) + H2O (g) → CO2 (g) + H2 (g)
use the following data :
Substance Cp(J/mol K) fH(298K) (kJ/mol)
CO 29 –110
H2O 33 –241
CO2 37 –393
H2 29 0
31. The heat of formation of one mole of HI from hydrogen and iodine vapour at
27° C is –8000cal.
1 1
H 2 (g) + I 2 (g) ⎯⎯
→ HI(g); H = – 800 cal.
2 2
Calculate the heat of formation at 127°C. Given
CP = 7 + 6 × 10–3 T for hydrogen (g) (Cal/mol/K)
CP = 7 + 4 × 10–3 T for iodine (g) (Cal/mol/K)
CP = 7 + 3 × 10–3 T for HI (g) (Cal/mol/K)
Misc
32. Froms the given table answer the following questions:
CO(g) CO2(g) H2O(g) H2(g)
(fH°)298 (kcal/mole) –26 –94 –57 0
(fG°)298 (kcal/mole) –32 –94 –54 0
S°298 (Cal/K/mole) 47 51 ? 31
Reaction : H2O(g) + CO(g) H2(g) + CO2(g)
(1) Calculate rH 298 (ii) Calculate rG 298
(iii) Calculate  r S298 (iv) Calculate  r U 298
(v) Calculate S298 [H2O(g)]
APNI KAKSHA 32
33. At temperatures above 85 K, decarboxylation of acetic acid becomes a spontaneous process

under standard state conditions. What is the standard entropy change (in J/K-mol) of the
reaction.
CH3COOH (aq) ⎯→ CH4(g) + CO2(g)
Given : H 0f [CH3COOH (aq)] = –484 kJ/mole
H 0f [CO2(g)] = –392 kJ/mole
H 0f [CH4(g)] = –75 kJ/mole
34. From the following data of H of the following reactions

C(s) + 1/2O2(g) ⎯→ CO(g) ; H = –110 kJ
and C(s) + H2O(g) ⎯→ CO(g) + H2(g) ; H = 130 kJ
The mole ratio of O2 & steam being passed over coke at 1273 K, so that temperature remains
constant is :
(A) 0.6 : 1 (B) 1.67 : 1 (C) 0.3 : 1 (D) 0.4 : 1
APNI KAKSHA 33
EXERCISE # O-II
1. Which of the following do(es) not represent H formation of the product.

1 1
(A) H2(g) + (aq) ⎯→ H+(aq) + e– (B) O3(g) ⎯→ O2(g)
2 2
(C) NH +4 + Cl–(g) ⎯→ NH4Cl(s) (D) P4(black) + 5O2 (g) ⎯→ P4O10(s)
2. Pick out the incorrect statement(s) among the following.
(A) Sof {He(g)} > 0 at 298 K (B) Sof {H2O(g)} > 0 at 298 K
(C) S° of H2 gas > 0 at 298 K (D) Gof {H2(g)} > 0 at 298 K
3. Select the correct option -

(A) Hf(H(g)) is equal to Hatomisation of H2(g)
(B) HBE(H–H) is equal to Hf of H(g)
(C) HBE(H–H) is equal to Hatomisation of H2(g)
(D) Hcombustion [H2(g)] is equal to Hf [H2O(l)] at 300K
4. Which of the following statement is (are) correct ?

(A) for any reaction rHº = fH° (product) – (fH0)R (reactant)
(B) H f of CO2 (g) is same as the H°comb. of carbon graphite(s)
(C) all exothermic reactions have a free energy change negative

(D) for a reaction N2(g) + O2(g) ⎯→ 2NO(g), the heat at constant pressure and the heat at
constant volume at a given temperature are same
5. (i) Cis–2 – butene → trans – 2 – butene, H1

(ii) Cis – 2 – butene → 1 – butene, H2
(iii) 9H1 + 5  H2 = 0
(iv) Enthalpy of combustion of 1–butene, H = –649.8 kcal/mol
(v) Enthalpy of combustion of trans 2 – butene, H = –647.0 kcal/mol.
The value of H1 & H2 in Kcal/mole are
(A) H1 = –1.0 (B) H2 = 1.8
(C) H1 = –2.0 (D) H2 = 2.8
APNI KAKSHA 34
6. From the following data at 25°C

Reaction rH° kJ/mol
1
H2(g) + O2(g) ⎯→ H2O(g) –242
2
H2(g) ⎯→ 2H(g) 436
O2(g) ⎯→ 2O(g) 495
Which of the following statement(s) is/are correct:
(A) rH° for the reaction H2O (g) ⎯→ 2H(g) + O(g) is 925.5 kJ/mol
(B) rH° for the reaction OH(g) ⎯→ H(g) + O(g) is 502 kJ/mol
(C) Enthalpy of formation of H(g) is 218 kJ/mol
(D) Enthalpy of formation of OH(g) is –121 kJ/mol
7. Which of the following mixture of strong acid & strong base will give same temperature change
for solution (Assume density & specific heat same for all solutions)-
(A) 50 ml 0.1 M HCl + 50 ml 0.1 M NaOH
(B) 30 ml 0.1 M HCl + 30 ml 0.1 M NaOH
(C) 25 ml 0.1 M H2SO4 + 50 ml 0.1 M KOH
(D) 50 ml 0.1 M H2SO4 + 50 ml 0.1 M NaOH
Paragraph for Q.8 to Q.9

Bond dissociation enthalpy of the first H–S bond in hydrogen sulphide is 376 kJ/mole.
The enthalpies of formation of H2S(g) and S(g) are –20.0 and 277.0 kJ/mole respectively.
The enthalpy of formation of gaseous hydrogen atom is 218 kJ/mole. Using above information,
answer following questions :
8. The enthalpy of formation of free radical HS is

(A) 138 kJ/mole (B) –138 kJ/mole
(C) –10 kJ/mole (D) 357 kJ/mole
9. The bond dissociation enthalpy of the free radical HS is

(A) 138 kJ/mole (B) 276 kJ/mole
(C) 357 kJ/mole (D) 376 kJ/mole
APNI KAKSHA 35
Paragraph for Q.10 to Q.11

Amount of heat evolved during complete combustion of liquid benzene can be calculated from
the following data.
(i) 18 gm of graphite on complete combustion evolve 591 kJ heat
(ii) H f (H2O,l) = – 286 kJ/mol
(iii) The heat of formation of liquid benzene is 50 kJ /mole
10. Heat of formation of CO2(g) from following data is-

(A) –286 kJ/mole (B) –590 kJ/mole (C) –394 kJ/mole (D) –3268 kJ/mole
11. Find heat evolved from combustion of 78 gm benzene

(A) 3272 kJ (B) 6345 kJ (C) 4536 kJ (D) 5364 kJ
Match the column :

12. Column–I Column–II
(A) C(graphite) + O2(g) → CO2(g) (P) H 0formation
(B) C(gaphite) ⎯→ C(gas) (Q) H 0combustion
(C) CH3COOH(aq) + OH– (aq) ⎯→ CH3COO– (aq) + H2O(l) (R) H 0atomization
(D) CH4(g) ⎯→ C(g) + 4H(g) (S) H 0neutralization
Match list
13. List-I List-II
(P) O2(g) (A) fHº = +ve fSº = +ve
(Q) O3(g) (B) fHº = –ve fSº = –ve
(R) Br2(g) (C) fHº = +ve fSº = –ve
(S) H2(l) (D) fHº = 0 fSº = 0
Code :
P Q R S
(A) 4 3 1 2
(B) 2 4 1 3
(C) 3 4 1 2
(D) 2 3 1 4
APNI KAKSHA 36
14. Match the enthalpy change (H) mentioned in list-II for 16 gm O2 with the various reaction in
list-I.
List-I List-II (H in kJ)
(P) 2C2H2 + 5O2(g) ⎯→ 4CO2(g) + 2H2O(l), –2601 kJ (A) –285.8
(Q) H2(g) + 1/2O2(g) ⎯→ H2O(g), – 285.8 kJ (B) –196.75
(R) 3FeO(s) + 1/2O2(g) ⎯→ Fe3O4(s), –302.4 kJ (C) –260.1
(S) Cgraphite + O2(g) ⎯→ CO2(g), –393.5 kJ (D) –302.4
Code :
P Q R S
(A) 4 1 3 2
(B) 3 1 4 2
(C) 3 4 1 2
(D) 2 3 1 4
APNI KAKSHA 37
EXERCISE # S-II
1. An stoichiometric mixture of ferric oxide & Al is used as solid rocket fuel . Calculate the fuel
value per gm & fuel value per CC of the mixture. Enthalpies of formation & densities are :
H 0f (Al2O3) = –399 k Cal/mole ; H 0f (Fe2O3) = –199 kCal / mole,
density of Fe2O3 = 5.2 g/cc ; density of Al = 2.7 g/cc.
2. The enthalpy of formation of C2H5OH(l) is –66 k Cal/mol. The enthalpy of combustion of CH3–
O–CH3 is –348 k Cal/mol. Given that the enthalpies of formation of CO2(g) and H2O(l) are –94 k
Cal/mol & –68 k Cal/mol respectively, calculate H for the isomerisation of ethanol to
methoxymethane. All data are at 25º C.
3. The enthalpy of combustion of acetylene is –312 kcal per mole. If enthalpy of formation of CO2
& H2O are –94 & –68 kcal per mole respectively, calculate C  C bond enthalpy.
Given that enthalpy of atomisation of C is 150 kcal per mole and H – H bond enthalpy and
C – H bond enthalpy is 103 kcal per mole and 93 kcal per mole respectively.
4. Calculate the mass of mercury which can be liberated from HgO at 25ºC by the treatment of
excess HgO with 41.84 kJ of heat at
(a) constant pressure
(b) constant volume
Given : H 0f (HgO, s) = –90.8 kJ mol–1 & M (Hg) = 200.6 g mol–1.
5. Find the bond enthalpy (in kJ/mol) of one "three centre two electron bond" in
B2H6 {B–H–B→2B(g) + H(g)} from the given data
H 0f [BH3 (g)] = 100 kJ/mole H 0f [B2H6 (g)] = 36 kJ/mole
Hatm2[B(s)] = 565 kJ/mole Hatm[H2(g)] = 436 kJ/mole
6. Calculate the bond enthalpy of the O–H bond in water at 298K using the information given
below :-
(A) fH0[H(g)] = 218 kJ/mol
(B) fH0[O(g)] = 249.2 kJ/mol
(C) fH0[H2O(g)] = –241.8 kJ/mol
Also, determine the U of the O–H bond in water at 298K. Assume ideal gas behaviour.
APNI KAKSHA 38
7. The enthalpy of formation of ethane, ethylene and benzene from the gaseous atoms are –2840,
–2275 and –5530 kJmol–1 respectively. Calculate the resonance energy of benzene. The bond
enthalpy of C–H bond is given as equal to +410 kJ/mol.
8. Calculate the enthalpy of combustion of methyl alcohol at 298 K from the following data
Bond C–H C–O O–H O=O C=O
Bond Enthalpy(kJ mol–1) 414 351.5 464.5 494 711
Resonance energy of CO2 = –143 kJ mol–1
Latent heat of vaporisation of methyl alcohol = 35.5 kJ mol–1.
Latent heat of vaporisation of water = 40.6 kJ mol–1.
APNI KAKSHA 39
EXERCISE # (JEE-MAIN)
1. If at 298 K the bond energies of C–H, C–C, C=C and H–H bonds are respectively 414, 347, 615
and 435 kJ mol–1, the value of enthalpy change for the reaction : [AIEEE-2003]
H2C = CH2(g) + H2(g) ⎯→ H3C–CH3(g) at 298 K
will be :-
(A) +125 kJ (B) –125 kJ (C) +250 kj (D)–250 kJ
2. The enthalpies of combustion of carbon and carbon monoxide are –393.5 and –283 kJ mol–1
respectively. The enthalpy of formation of carbon monoxide per mole :- [AIEEE-2004]
(A) 110.5 kJ (B) 676.5 kJ (C) –676.5 kJ (D) –110.5 kJ
3. If the bond dissociation energies of XY, X2 and Y2 (all diatomic molecules) are in the ratio of
1 : 1 : 0.5 and fH for the formation of XY is –200 kJ mol–1. The bond dissociation energy of X2
will be :- [AIEEE-2005]
(A) 200 kJ mol–1 (B) 100 kJ mol–1 (C) 800 kJ mol–1 (D) 300 kJ mol–1
4. The enthalpy changes for the following processes are listed below : [AIEEE-2006]
Cl2(g) ⎯→ 2Cl(g), 242.3 kJ mol–1
I2(g) ⎯→ 2I(g) 151.0 kJ mol–1
ICl(g) ⎯→ I(g) + Cl(g), 211.3 kJ mol–1
I2(s) ⎯→ I2(g), 62.76 kJ mol–1
Given that the standard states for iodine and chlorine are I2(s) and Cl2(g), the standard
enthalpy of formation for ICl(g) is :-
(A) –16.8 kJ mol–1 (B) +16.8 kJ mol–1 (C) +244.8 kJ mol–1 (D) –14.6 kJ mol–1
5. The standard enthalpy of formation (fH°) at 298K for methane, CH4(g), is –74.8 kJ mol–1.
The additional information required to determine the average energy for C–H bond formation
would be:- [AIEEE-2006]
(A) Latent heat of vapourization of methane
(B) The first four ionization energies of carbon and electron gain enthalpy of hydrogen
(C) The dissociation energy of hydrogen molecule H2
(D) The dissociation energy of H2 and enthalpy of sublimation of carbon
APNI KAKSHA 40
6. Oxidising power of chlorine in aqueous solution can be determined by the parameters

indicated below:
1
1 diss H eg H hyd H
Cl2 (g) ⎯⎯⎯⎯
2
→ Cl(g) ⎯⎯⎯ → Cl− (g) ⎯⎯⎯ → Cl− (aq) [AIEEE-2008]
2
1
The energy involved in the conversion of Cl2(g) to Cl– (aq)
2
(using the data diss H Cl2 = 240 kJ mol–1, eg HCl = –349 kJ mol–1, hyd HCl– =
–381 kJ mol–1) will be:-
(A) –610 kJ mol–1 (B) –850 kJ mol–1 (C) +120 kJ mol–1 (D) +152 kJ mol–1
7. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer. The reaction is
3
CH3OH(l) + O2(g) ⎯→ CO2(g) + 2H2O(l)
2
At 298 K standard Gibb's energies of formation for CH3OH(l), H2O(l) and CO2(g) are –166.2,
–237.2 and –394.4 kJ mol–1 respectively. If standard enthalpy of combustion of methanol is
–726 kJ mol–1, efficiency of the fuel cell will be [AIEEE-2009]
(A) 90% (B) 97% (C) 80% (D) 87%
8. +
(
On the basis of the following thermochemical data : G 0f H(aq) =0 )
H2O(l) → H+(aq) + OH– (aq) ; H = 57.32 kJ
1
H2(g) + O2(g) → H2O (l) ; H = –286.20 kJ
2
The value of enthalpy of formation of OH– ion at 25°C is :- [AIEEE-2009]
(A) +228.88 kJ (B) –343.52 kJ (C) –22.88 kJ (D) –228.88 kJ
9. The standard enthalpy of formation of NH3 is –46.0 kJ mol–1. If the enthalpy of formation of H2
from its atoms is –436 kJ mol–1 and that of N2 is –712kJ mol–1, the average bond enthalpy of N–
H bond in NH3 is :- [AIEEE-2010]
(A) –1102 kJ mol–1 (B) –964 kJ mol–1 (C) + 352 kJ mol–1 (D) +1056 kJ mol–1
10. Consider the reaction : [AIEEE-2011]
4NO2(g) + O2(g) → 2N2O5(g), rH = –111kJ.
If N2O5(s) is formed instead of N2O5(g) in the above reaction, the rH value will be :-
(given, H of sublimation for N2O5 is 54 kJ mol–1)
(A) –165 kJ (B) +54 kJ (C) +219 kJ (D) –219 kJ
APNI KAKSHA 41
11. The enthalpy of neutralisation of NH4OH with HCl is –51.46 kJ mol–1 and the enthalpy of
neutralisation of NaOH with HCl is –55.90 kJ mol–1. The enthalpy of ionisation of NH4OH is:
[JEE-MAINS (online) 2012]
(A) +107.36 kJ mol–1 (B) –4.44 kJ mol–1 (C) –107.36 kJ mol–1 (D) +4.44 kJ mol–1
12. Given [JEE-MAINS (OnLine) 2013]

Reaction Energy Change (in kJ)
Li(s) ⎯→Li(g) 161
Li(g) ⎯→Li+(g) 520
1
F2(g) ⎯→ F(g) 77
2
F(g) + e– ⎯→ F– (g) (Electron gain enthalpy)
Li+(g) + F–(g) ⎯→ LiF(s) –1047
1
Li(s) + F2(g) ⎯→ Li F(s) –617
2
Based on data provided, the value of electron gain enthalpy of fluorine would be :
(A) –300 kJ mol–1 (B) –328 kJ mol–1 (C) –350 kJ mol–1 (D) –228 kJ mol–1
13. Given : [JEE-MAINS (online) 2013]

1
(a) H2 (g) + O2 (g) → H2O (l) ; Hº298K = –285.9 kJ mol–1
2
1
(b) H2(g) + O2 (g) → H2O (g) ; Hº298K = – 241.8 kJ mol–1
2
The molar enthalpy of vapourisation of water will be :-
(A) 241. 8 kJ mol–1 (B) 527.7 kJ mol–1 (C) 44.1 kJ mol–1 (D) 22.0 kJ mol–1
14. The standard enthalpy of formation (fHº298) for methane, CH4 is– 74.9 kJ mol–1.
In order to calculate the average energy given out in the formation of a C–H bond from this it is
necessary to know which one of the following? [JEE-MAINS(online) 2014]
(A) the dissociation energy of the hydrogen molecule, H2.
(B) the dissociation energy of H2 and enthalpy of sublimation of carbon (graphite).
(C) the first four ionisation energies of carbon and electron affinity of hydrogen.
(D) the first four ionisation energies of carbon.
APNI KAKSHA 42
15. For complete combustion of ethanol, C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l), the amount of
heat produced as measured in bomb calorimeter, is 1364.47 kJ mol–1 at 25ºC.
Assuming ideality the Enthalpy of combustion, cH, for the raction will be :-
(R = 8.314 kJ mol–1) [JEE-MAINS 2014]
(A) –1460.50 kj mol–1 (B) – 1350.50 kJ mol–1
(C) – 1366.95 kJ mol–1 (D) – 1361.95 kJ mol–1
16. The heat of atomisation of methane and ethane are 360 kJ/mol and 620 kJ/mol, respectively.
The longest wavelength of light capable of breaking the C–C bond is :
(Avogadro number = 6.02 × 1023, h = 6.62 × 10–34 J s) [JEE-MAINS (Online) 2015]
(A) 2.48 × 103 nm (B) 1.49 × 103 nm (C) 2.49 × 104 nm (D) 2.48 × 104 nm
17. The heats of combustion of carbon and carbon monoxide are –393.5 and –283.5 kJ mol–1,
respectively. The heat of formation (in kJ) of carbon monoxide per mole is :
[JEE-MAINS 2016]
(A) 676.5 (B) – 676.5 (C) –110.5 (D) 110.5
18. Given
C(graphite) + O2 (g) → CO2 (g) ; rH° = – 393.5 kJ mol–1
1
H2(g) + O2(g) → H2O (l) ; rH° = – 285.8 kJ mol–1
2
CO2 (g) + 2H2O (l) → CH4 (g) + 2O2 (g) ; rH° = + 890.3 kJ mol–1
Based on the above thermochemical equations, the value of rH° at 298 K for the reaction
C(graphite) + 2H2(g) → CH4 (g) will be: [JEE-MAINS 2017]
(A) +74.8 kJ mol–1 (B) +144.0 kJ mol–1 (C) –74.8 kJ mol–1 (D) –144.0 kJ mol–1
19. The combustion of benzene (l) gives CO2(g) and H2O (l). Given that heat of combustion of
benzene at constant volume is – 3263.9 kJ mol–1 at 25º C ; heat of combustion (in kJ mol–1)
of benzene at constant pressure will be : (R = 8.314 JK–1 mol–1) [JEE-MAINS 2018]
(A) – 3267.6 (B) 4152 . 6 (C) –452. 6 (D) 3260
APNI KAKSHA 43
20. Given:
(i) C (graphite) +O2 ( g) → CO2 ( g); ΔrH ∘ = xkJmol−1
1
(ii) C (graphite) + 2 O2 ( g) → CO2 ( g); ΔrH ∘ = ykJ mol
1
(iii) CO(g) + 2 O2 ( g) → CO2 ( g); ΔrH ∘ = zkJmol−1
Based on the above thermochemical equations, find out which one of the following algebraic
relationships is correct ? [JEE-MAINS 2019 (Jan.)]
(A) x = y–z (B) y = 2z–x (C) z = x + z (D) x = y + y
21. Enthalpy of sublimation of iodine is 24 cal g–1 at 200ºC. If specific heat of I2(s) and I2(vap) are
0.055 and 0.031 cal g–1 K–1 respectively, then enthalpy of sublimation of iodine at 250ºC in cal
g–1 is: [JEE-MAINS 2019 (Apr.)]
(A) 2.85 (B) 22.8 (C) 11.4 (D) 5.7
22. The internal energy change (in J ) when 90 g of water undergoes complete evaporation at
100∘ C is (Given : ΔHvap for water at 373 K = 41 kJ/mol, 𝑅 = 8.314JK −1 mol−1 )
[JEE-MAINS 2020]
23. Lattice enthalpy and enthalpy of solution of NaCl are 788kJmol−1 and 4kJmolJm−1, respectively.
The hydration enthalpy of NaCl is [JEE-MAINS 2020]
(A) 784kJmol−1 (B) −780kJmol−1 (C) 780kJmol−1 (D) −784 kJ mol−1
24. According to the following diagram, 𝐴 reduces CO2 when the temperature is :
[JEE-MAINS 2020]
(A) > 1400∘ C (B) < 1400∘ C

(C) > 1200∘ C but < 1400∘ C (D) < 1200∘ C
25. The first and second ionisation enthalpies of a metal are 496 and 4560 kJ mol−1 , respectively.
How many moles of HCl and H2 SO4 , respectively, will be needed to react completely with 1
mole of the metal hydroxide? [JEE-MAINS 2020]
(A) 1 and 0.5 (B) 2 and 0.5 (C) 1 and 2 (D) 1 and 1
APNI KAKSHA 44
26. For the reaction

C2H6 → C2H4 + H2
the reaction enthalpy rH = ______ kJ mol–1.
(Round off to the Nearest Integer).
[Given : Bond enthalpies in kJ mol–1 : C–C : 347, C=C : 611; C–H : 414, H–H : 436]
[JEE Main, March 2021]
27. The Born-Haber cycle for KCl is evaluated with the following data:
[JEE Main, August 2021]
 f H– for KCl = – 436.7 kJ mol–1 ;

 sub H–for K = 89.2 kJ mol–1;
 ionization H– for K = 419.0 kJ mol–1;
 electron gain H– for Cl(g) = – 348.6 kJ mol–1;
 bond H– for Cl2 = 243.0 kJ mol–1;
The magnitude of lattice enthalpy of KCl in kJ mol–1 is _______ (Nearest integer)
28. At 25C and 1 atm pressure, the enthalpy of combustion of benzene (A) and acetylene (g) are –
3268 kJ mol–1 and –1300 kJ mol–1, respectively. The change in enthalpy for the reaction 3
C2H2(g) → C6H6(l), is [JEE Main, June 2022]
(A) + 324 kJ mol–1 (B) +632 kJ mol–1
(C) – 632 kJ mol–1 (D) – 732 kJ mol–1
29. 2.4 g coal is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1 atm pressure.
The temperature of the calorimeter rises from 298 K to 300 K. The enthalpy change during the
combustion of coal is – x kJ mol–1. The value of x is ___________. (Nearest integer)
(Given : Heat capacity of bomb calorimeter 20.0 kJ K–1. Assume coal to be pure carbon)
[JEE Main, July 2022]
30. While performing a thermodynamics experiment, a student made the following observations,
HCl + NaOH → NaCl+ H2O H = –57.3 kJ mol–1
CH3COOH + NaOH → CH3COONa + H2O H = –55.3 kJ mol–1.
The enthalpy of ionization of CH3COOH as calculated by the student is________ kJ mol–1.
(Nearest integer) [JEE Main, July 2022]
APNI KAKSHA 45
31. When 600 mL of 0.2 M HNO3 is mixed with 400 mL of 0.1M NaOH solution in a flask, the rise in
temperature of the flask is _________ × 10–2 0C.
(Enthalpy of neuralization = 57 kJ mol–1 and specific heat of water = 4.2 JK–1 g–1)
(Neglect heat capacity of flask) [JEE Main, July 2022]
APNI KAKSHA 46
EXERCISE # (JEE-ADVANCE)
1. Estimate the average S–F bond enthalpy in SF6. The H°f values of SF6 (g), S(g), and F (g) are –
1100 , 275 and 80 kJ/mol respectively. [JEE 1999]
2. Which of the following is not an endothermic reaction? [JEE 1999]

(A) Combustion of methane
(B) Decomposition of water
(C) Dehydrogenation of ethene to acetylene
(D) Conversion of graphite to diamond
3. Diborane is a potential rocket fuel which undergoes combustion according to the reaction,
B2H6(g) + 3O2(g) ⎯→ B2O3(s) + 3H2O(g)
From the following data, calculate the enthalpy change for the combustion of diborane :
[JEE 2000]
3
2B(s) + O2(g) ⎯→ B2O3(s) ; H = –1273 kJ
2
1
H2(g) + O2(g) ⎯→ H2O(l) ; H = –286 kJ
2
H2O(l) ⎯→ H2O(g) ; H = 44 kJ
2B(s) + 3H2(g) ⎯→ B2H6(g) ; H = 36 kJ
4. H°f for CO2(g), CO(g) and H2O(g) are – 393.5, –110.5 and –241.8 kJ mo–l respectively.
The standard enthalpy change (in kJ) for the reaction [JEE 2000]
CO2(g) + H2(g) ⎯→ CO(g) + H2O (g) is
(A) 524.1 (B) 41.2 (C) –262.5 (D) – 41.2
5. Which of the following reactions defines H°f ?

(A) C(diamond) + O2(g) ⎯→ CO2(g) (B) 1/2 H2(g) + 1/2 F2(g) ⎯→ HF(g)
(C) N2(g) + 3H2(g) ⎯→ 2NH3 (D) CO(g) + 1/2O2(g) ⎯→ CO2(g) [JEE 2003]
6. In a constant volume calorimeter, 3.5 g of a gas with molecular weight 28 was burnt in excess
oxygen at 298.0 K. The temperature of the calorimeter was found to increase from 298.0 K to
298.45 K due to the combustion process. Given that the heat capacity of the calorimeter is
2.5 kJ K–1, the numerical value for the enthalpy of combustion of the gas in kJ mol–1 is
[JEE 2009]
APNI KAKSHA 47
7. Using the data provided, calculate the multiple bond energy (kJ mol–1) of a C  C bond in
C2H2. That energy is (take the bond energy of a C–H bond as 350 kJ mol–1.) [JEE 2012]
2 C(s) + H2(g) ⎯→ C2H2(g) H = 225 kJ mol–1
2 C(s) ⎯→ 2C(g) H = 1410 kJ mol–1
2 C(s) ⎯→ 2C(g) H = 1410 kJ mol–1
H2 (g) ⎯→ 2H(g) H = 330 kJ mol–1
(A) 1165 (B) 837 (C) 865 (D) 815
8. The standard enthalpies of formation of CO2(g), H2O(l) and glucose(s) at 25ºC are
–400 kJ/mol, –300 kJ/mol and –1300 kJ/mol, respectively. The standard enthalpy of
combustion per gram of glucose at 25ºC is [JEE (Advance)2013]
(A) +2900 kJ (B) – 2900 kJ (C) –16.11 kJ (D) + 16.11 kJ
9. Choose the reaction(s) from the following options, for which the standard enthalpy of reaction
is equal to the standard enthalpy of formation. [JEE (Advance)2019]
(A) 2H2 (g) + O2(g) → 2H2O(l) (B) 2C(g) + 3H2(g) → C2H6(g)
1 3
(C) S8(s) + O2(g) → SO2(g) (D) O2(g) → O3(g)
8 2
10. Tin is obtained from cassiterite by reduction with coke. Use the data given below to determine
the minimum temperature (in K) at which the reduction of cassiterite by coke would take place.
At 298 K: Δf H 0 (SnO2 (s)) = −581.0 kJ mol−1 , Δf H 0 (CO2 (g)) = −394.0 kJ mol−1 ,
S 0 (SnO2 (s)) = 56.0 J K −1 mol−1 , S 0 (Sn(s)) = 52.0 J K −1 mol−1 ,
S 0 (C(s)) = 6.0 J K −1 mol−1 , S 0 (CO2 ( g)) = 210.0 J K −1 mol−1 .
Assume that the enthalpies and the entropies are temperature independent.
[JEE (Advance)2020]
11. 2 mol of Hg(g) is combusted in a fixed volume bomb calorimeter with excess of O2 at 298 K and
1 atm into HgO (s). During the reaction, temperature increases from 298.0 K to 312.8 K. If heat
capacity of the bomb calorimeter and enthalpy of formation of Hg(g) are 20.00 kJ K −1 and
61.32 kJ mol−1 at 298 K, respectively, the the calculated standard molar enthalpy of formation
of HgO(s) at 298 K is XkJ mol−1 . The value of |X| is _________ . [JEE (Advance)2022]
[Given: Gas constant R = 8.3 J K −1 mol−1 ]
APNI KAKSHA 48
ANSWER KEY
EXERCISE O-I
1. (B) 2. (D) 3. (C) 4. (D) 5. (D) 6. (A)
7. (B) 8. (D) 9. (D) 10. (D) 11. (A) 12. (C)
13. (B) 14. (C) 15. (B) 16. (C) 17. (D) 18. (B)
19. (B) 20. (B) 21. (B) 22. (B) 23. (A) 24. (D)
25. (D) 26. (A) 27. (B) 28. (A) 29. (C) 30. (B)
31. (C) 32. (B) 33. (C)
EXERCISE S-I
1. (–266 kJ/mol and –825 kJ/mol)
2. (– 88 kJ/mol) 3. (129 kJ) 4. (–1560.1 kJ mol–1)
5. (25.66 days)
6. ((i) - 3201 kJ/mol (ii) - 3199.75 kJ/mol)
7. ((i) - 885 kJ/mol (ii) - 889.95 kJ/mol) 8. (3.69 mol % CH4)
9. (132.5 kJ/mol) 10. (400 kJ/mole)
11. (– 119 kJ/mol) 12. (+20.6 k Cal) 13. (-266 kJ mol–1)
14. (213 kJ / mol) 15. (275 kJ/mol) 16. (- 72 kJ mol–1)
17. (292 kcal/mol) 18. (–392 kJ mol–1)19. (– 90.75 kcal mol–1)
20. (for Cl– –384 kJ mol–1, for I– –307 kJ mol–1)
21. (–19 kCal/mole)
22. (– 80 kJ/mole) 23. (-255 kJ/mol) 24. (84)
25. (–2669) 26. (— 1410 Cal)
27. (480 J) 28. (–31.5 kJ/mole) 29. (2 kcal)
30. (H = – 41.192 kJ) 31. (–8070 cal)
32. ((i) – 11 kCal/mole; (ii) – 8 kCal/mole, (iii) – 10.067 Cal / K mole, (iv) –11 kCal/mole,
(v) + 45.067Cal/ K mole)
33. (200 J/K mole)
34. (A)
EXERCISE O-II
1. (A,B,C,D) 2. (A,B,D) 3. (C,D) 4. (A,B,D) 5. (A,B)
6. (A,C) 7. (A,B,D) 8. (A) 9. (C) 10. (C)
11. (A) 12. 𝐀 → 𝐏, 𝐐 ; 𝐁 → 𝐏, 𝐑 ; 𝐂 → 𝐒, 𝐃 → 𝐑 13. (A)
14. (B)
APNI KAKSHA 49
EXERCISE S-II
1. (0.9345 k Cal g–1, 3.94 kCal cm–3) 2. (22kCal mol–1)
3. (EC  C = 161 kcal/mol) 4. ((a) 92.435 g (b) 93.715 g)
5. (EB–H–B = 455 kJ/mole)
6. (H (O–H) = 463.5 kJ/mol U = 461 kJ/mol)
7. (– 25 kJ/mol) 8. (– 669.7 kJ mol–1)
JEE MAIN
1. (B) 2. (C) 3. (C) 4. (A) 5. (D) 6. (A)
7. (B) 8. (D) 9. (C) 10. (D) 11. (D) 12. (B)
13. (C) 14. (B) 15. (C) 16. (B) 17. (C) 18. (C)
19. (A) 20. (D) 21. (B) 22. (189494) 23. (D)
24. (A) 25. (A) 26. (128) 27. (718) 28. (C) 29. (200)
30. (B) 31. (54)
JEE ADVANCED
1. (309.16kJ/mol) 2. (A) 3. (–2035kJ mol–1) 4. (B)
5. (B) 6. (9) 7. (D) 8. (C) 9. (C,D)
10. (935) 11. (90.39)
APNI KAKSHA 50
SOLUTION
EXERCISE O-I
3 1
1. C(graphite,s) + H2(g) + Cl2(g) ⎯→ CH3Cl(g)
2 2
2. rH = –944.7 – 4 × 92.3 + 763.2 + 2 × 241.8 = –67.1 kJ
3. –890.4 = –393.5 – 2 × 285.9 – Hf + CH4(g)

Hf CH4(g) = –74.9 kJ
4. –40 = 2Hf NH3 – Hf N2H4(g)

–40 = 2 Hf NH3(g) + 120
2Hf NH3(g) = –160  Hf NH3(g) = –80 kJ
5. –2601 = – 4 × 394 – 2 × 285.8 – 2 Hf C2H2

2Hf C2H2 = 453.4
Hf C2H2 = 226.7 kJ
H 3
6. Hf HCl(g) =
2
H 2
Hf NH3(g) =
2
–H1 = Hf NCl3(g) + 3Hf HCl(g) – Hf NH3(g)
3 H 2
–H1 = Hf NIl3(g) + H3 –
2 2
H 2 3
Hf NCl3(g) = – H3 – H1
2 2
7. A ⎯→ B H = + 100 Kcal
Hf B > Hf A
B ⎯→ C H = –80 Kcal
Hf B > Hf C
A ⎯→ C H = + 20 Kcal
Hf C > Hf A
 Hf B > Hf C > Hf A
APNI KAKSHA 51
8. C3H8(g) + SO2(g) ⎯→ 3CO2(g) + 4 H2O(l)

–2221.6 = – 3 × 394 – 4 × 285.8 – Hf C3H8(g)
Hf C3H8(g) = 103.6 kJ
0.5  2 1000
U 0f NO2(g) = − = +8 Kcal mol–1
1000
1939.1
9. H = − 12 = –1939.1 × 0.3 kJ= –581.73 kJ
40
1
10. 2H(g) + O2(g) ⎯→ H2O(g)
2
1 −242
H2(g) + O2(g) ⎯⎯⎯ → H2O(g)
2
Resonating
R.H. 6C(g) + 6H(g)
Structure
= – 242
rH1 = – 678 kJ
rH1 678
= = 2.8
rH 2 242
11. from (d) Hƒ H2O() = – 285 kJ

(a) 2NH3(g) + 3N2O(g) ⎯→ 4N2(g) + 3H2O() rH = –1011 kJ
3Hƒ H2O() – 2Hƒ NH3(g) – 3Hƒ N2O(g) = –1011
2Hƒ NH3(g) + 3Hƒ N2O(g) = – 3 × 285 + 1011= 156 (i)
(b) N2O(g) + 3H2(g) ⎯→ N2H4() + H2O() rH = – 317 kJ
Hƒ N2H4() – Hƒ N2O(g) + Hƒ H2O()= – 317 kJ
Hƒ N2H4() – Hƒ N2O(g) = –32 (ii)
APNI KAKSHA 52
(c) 4NH3(g) + O2(g) ⎯→ 2N2H4() + 2H2O() rH = –286 kJ
2Hƒ N2H4() + 2Hƒ H2O() – 4Hƒ NH3(g) = –286 kJ
2Hƒ N2H4() – 4Hƒ NH3(g) = 284 (iii)
from (i), (iii) and (iii)
Hƒ N2H4() = 50.5 kJ/mol
Hƒ N2O(g) = 82.5 kJ/mol

Hƒ NH3(g) = – 45.75 kJ/mol
rH = 3Hƒ H2O() – Hƒ N2H4()
= – 3 × 285 – 50.5
= – 620.5 kJ/mol
12. (i) H2(g) + Cl2(g) ⎯→ 2HCl(g)
rH300K = –184.5
(ii) 2H2(g) + O2(g) ⎯→ 2H2O(g)
rH300K = –483 kJ/mol
(iii) 4HCl(g) + O2(g) ⎯→ 2Cl2(g) + 2H2O(g)
(iii) = (ii) – 2 × (i)
rH3 = rH2 – 2 × rH1= –483 + 2 × 184.5= –114 kJ/mol
H = U + ng RT
−1 8.3  300

–114 = U +
1000
U = –111.5 kJ/mol
13. Hf HCl(g) = –92 kJ/mol
Hf Na2SO4(s) = –1382 kJ/mol
Hf H2SO4(l) = –811 kJ/mol
Hf NaCl(s) = –411 kJ/mol
rH = – 2 × 92 – 1382 + 811 + 2 × 411= 67 kJ/mol
H = U + ng RT
2  8.3  300
67 = U +  U = 62.02 kJ/mol
1000
APNI KAKSHA 53
14. –16 = 2 – 2 U 0f NO2(g)

U 0f NO2(g) = 9 Kcal mol–1
1
N2(g) + O2(g) ⎯→ NO2(g)
2
ng = –0.5
1 1
15. H2(g) + Cl2(g) ⎯→ HCl(g)
2 2
1 1
rH = × 104 + × 58 – 103= –22.0 Kcal
2 2
16. ClF3(g) ⎯→ Cl(g) + 3F(g)
rH = 3 Cl–F = 513 kJ
Cl–F = 171 kJ
17. CH4(g) + Cl2(g) ⎯→ CH3Cl(g) + HCl(g)
rH = 4 × C–H + Cl–Cl – 3 × C–H – 3 × C–H – C–Cl – H–Cl
–25 = x + y – 84 – 103
x 9
x + y = 162 and =
y 5
2.8 y = 162 x = 1.8 y
Cl–Cl = y = 57.75
18. Na+(g) + I–(g)
RE
–5505
x2
rH2 = x1 + – 2x3
2
x2
rH1 = x1 + – 2x3 – x4
2
19. Form step-1 rH = O–H
Form step-2 rH = O–H
2O–H = 498 + 428
O–H = 463 kJ/mol

APNI KAKSHA 54
20. + 699 (g)
rH = 3 C–C – C–C – C=C
= 2 C–C – C=C = 2 × 348 – 615= + 81 kJ/mol
21. 5C(s) + 4H2(g) ⎯→ H2C = C — C = CH2(g)
101 5C(s) + 4H2(g) ⎯→ H2C = C — C = CH2(g)

–390
2 = 772 + Hhyd Na+(g) + Hhyd Cl–(g)
3
–770 = Hhyd Cl–(g) + Hhyd Cl–(g)
2.5
−770  2.5
Hhyd Cl–(g) = = –350 kJ/mol
5.5
22. HCl (aq.) ⎯⎯→ HCl (aq.) –2.5
4M 2M
1000 5 mole
HCl (aq.) ⎯⎯→ HCl(aq.)

4M 2M
500 ml
23.
rH = – 140 – 115= –255
APNI KAKSHA 55
–255 = –RE –264  RE = 255 – 264= –9 kJ

28. H+ (aq) + OH– (aq) ⎯→ H2O(l)
–57.3 = –285.8 – H 0f OH– (aq)
H 0f OH– (aq) = –285.8 + 57.3= –228.5 kJ/mol
29. Cp, m (B) = 300 J/mol
Cp, m (C) = 200 J/mol
Cp, m (A) = 150 J/mol
(Cp)r = 3 × 200 – 150 – 2 × 300 = –150 J/mol
150  10
rH310K + 10 = −
1000
rH310K = –10 – 1.5 = –11.5 kJ/mol
30. rG° = G 0f PCl3(g) – G 0f PCl5(g)
= – 60 + 74 = + 14 Kcal/mol
rG° = –RT ln k
2  1000
14 = − ln k
1000
–7 = ln k
– 10 ln2 = ln k  k = 2–10
31. (i) Au(OH)3 + 4HCl ⎯→ HAuCl4 + 3H2O H = 28 kcal

(ii) Au(OH)3 + 4HBr ⎯→ HAuBr4 + 3H2O H = – 36.8 kcal
(i) – (ii) = (iii)
(iii) HAuBr4 + 4HCl ⎯→ HAuCl4 + 4HBr rH = 64.8 kcal
0.44
% conversion of HAuBr4 =  100 = 0.6 %
64.8
33. C (graphite, s) ⎯→ C (diamond, s) rH1 = 1.9 kJ

C (diamond, s) + O2(g) ⎯→ CO2(g) rH2
C (diamond, s) + O2(g) ⎯→ CO2(g) rH3
APNI KAKSHA 56
rH3=rH1 – rH2
C (diamond, s) ⎯→ C (graphite, s)
APNI KAKSHA 57
EXERCISE S-I
1. From reaction (D)
1
CO (g) + O2(g) ⎯→ CO2(g)
2
H = –282 kJ
–282 = Hf CO2 (g) – Hf CO (g)
From reaction (C)
Hf CO2 (g) = –393 kJ
–282 = –393 – Hf CO (g)
Hf CO (g) = –393 + 282= –111 kJ/mol
Form reaction (B)
155 = Hf CO (g) – Hf FeO (s)
Hf FeO(s) = –111 –155= –266 kJ/mol
492 = –3 × 111 – Hf Fe2O3(s)
Hf Fe2O3(s) = –333 – 492= –825 kJ
2. C2H6 (g) + 3.5 O2 (g) ⎯→ 2 CO2(g) + 3 H2O(l)

3120
H = − = –1560 kJ
2
–1560 = –2 × 395 – 3 × 286 – Hf C2H6 (g)
Hf C2H6 (g) = –2 × 395 – 3 × 395 – 3 × 286 + 1560
Hf C2H6 (g) = –88 kJ
3. CS2 (l) + 2O2(g) ⎯→ CO2(g) + 2 SO2(g)

HC C (graphite, s) = Hf CO2 (g)
HC S (rhombic, s) = Hf SO2 (g)
–1108 = Hf CO2 (g) + 2 Hf SO2 (g) – Hf CS2(l)
–1108 = –393 – 2 × 293 – Hf CS2 (l)
Hf CS2 (l) = –393 – 2 × 293 + 1108= 129 kJ mol–1

4. C3H8 (g) + H2(g) ⎯→ C2H6(g) + CH4(g)
–55.7 = HC C3H8 (g) + HC H2 (g) –HC C2H6 (g) + HC H2 (g)
–55.7 = –2220 + 285.5 –HC C2H6 + 890
HC C2H6 = –2220 + 285.5 + 890 + 55.7= –1560.1 kJ/mol

APNI KAKSHA 58
5. q = +2658 kJ/mol
11.2 103
moles of butane =
58
11.2 103
total heat released = × 2658 kJ
58
11.2 103
20,000 × n =  2658
58
11.2  2658
n= = 25.66
20  58
15
6. C6H5 COOH(s) + O2 (g) ⎯→ CO2 (g) + 3H2O(l)
2
rH = 7Hf CO2 (g) + 3Hf H2O (l) –Hf C6H5 COOH(s)
= – 7 × 393 – 3 × 286 + 408
qp = H = –3201 kJ/mol
qv = U
0.5  8.314  300

H = U + ngRT –3201 = U –
1000
0.5  8.314  300

U = –3201 + = –3199.75 kJ/mol
1000
7. q = 0.5 × 17.7 kJ
−0.5 17.7
H =  16 = –885 kJ mol–1
0.16
CH4(g) + 2O2(g) ⎯→ CO2(g) + 2H2O(l)
2  8.314  300
H = –885 – = –889.95 kJ/mol
1000
8. q = 1200 × 0.25 = 300 cal

q = 200 Kcal mol–1
300
nCH4 = = 1.5 × 10–3
200 103
nT = 1 ×1 = 0.0406
0.0821 × 300 = 0.406 × 10–3
1.5 10−3 15
mole % of CH4 = −3
100 = = 3.69 %
0.406 10 4.06
APNI KAKSHA 59
9. XeF2(g) + H2(g) ⎯→ 2HF(g) + Xe(g) ; rH = –430 kJ

rH = 2 × Xe–F + H–H –(2 × H–F)
–430 = 2 × Xe–F + 435 – 2 × 265
Xe–F = + 132.5 kJ/mol
10. N2H4(g) ⎯→ N2H2(g) + H2(g)

rH = 4 N–H + N–N – N=N – 2 × N–H – H–H
109 = 2 × 391 + 163 – N=N – 436
N=N = 2 × 391 + 163 – 436 – 109 = + 400 kJ mol
11. C2H4(g) + H2(g) ⎯→ C2H6(g)

rH = 4 × C–H + C=C + H–H – [C–C + 6 C–H]
= 606 + 431 – 336 – 2 × 410 = –119 kJ/mol
12.
5C(g) + 8H(g) ⎯→ C5H8(g)
rH = 5 × 121 + 4 × 104 – (2 C=C + 2 C–C + 8 C–H)
= 5 × 171 + 4 × 104 – (2 × 147 + 2 × 83 + 8 × 98.8) = 20.6 Kcal
13. H–H = 2 × 218 kJ/mol

O–O = 2 × 249 kJ/mol
H atom. C(s) = 715 kJ/mol
rH1 + 38 = 715 + 4 × 218 + 249 – (3 × C–H + C–O + O–H)
APNI KAKSHA 60
rH1 + 38 = 715 + 4 × 218 + 249 – (3 × 415 + 356 + 463)
rH1 = –266 kJ/mol
14. PH3(g) ⎯→ P(g) + 3H(g)

H atom. PH3(g) = 3 P–H = 95.4
954
P–H = = 318 kJ/mol
3
P2H4(g) ⎯→ 2P(g) + 4H(g)
H atom. P2H4(g) = P–P + 4P–H = 1485
P–P = 1485 – 4 × 318 = + 213 kJ mol–1
15. C2H5 – S – S – C2H5(g) ⎯→ C2H5 – S – C2H5(g) + S(g)

rH = –150 + 225 + 200 = +275 kJ/mol
rH = S–S = +275 kJ/mol
16. n CH2 = CH2 ⎯→ {CH2 – CH2}n

rH = C=C – 2C–C = 590 – 2 × 331= –72 kJ/mol
17. XeF4 (g) ⎯→ Xe+ (g) + F– (g) + F2(g) + F(g)

rH = 4 × Xe – F + I.E. Xe(g) – egH F(g) – F – F
= 4 × 34 + 279 – 85 – 38 = + 292 Kcal / mol
18.
–571 = 101 + 494 + 80 + egH F(g) – 894
egH F(g) = –392 kJ/mol
19. –105 = 20.5 + 28.75 + X +  – 159.5 = – 90.75 kcal/mol
APNI KAKSHA 61
20.
–2 = +772 – 390 + H hyd Cl–(g)
H hyd Cl– (g) = – 2 + 390 – 172 = – 384 kJ/mol
+2 = 699 – 390 + H hyd I–(g)
H hyd I–(g) = –307 kJ/mol
21.
–16 = 3 + rH
rH = –19 Kcal
22. HCl(g) + aq ⎯→ HCl (aq) ⎯→ H+ (aq) + Cl– (aq)

rH = Hf Cl–(aq) – Hf HCl (g)
= –170 + 90= –80 kJ/mol
23.
–390 = 715 + 500 – 2 × 875 + RE
RE = –390 + 2 × 675 – 715 – 500 = –255 kJ/mol
APNI KAKSHA 62
24.
–116.2 = – RE – 7 × 28.6
RE = –7 × 28.6 + 116.2= –84 Kcal mol–1
25.
rH1 + 4 × 41 = rH2 – 3 × 143
rH2 = 2 C–C + 8 C–H + 5 O=O – 3 × 2 × C=O – 4 × 2 × O–H
rH2 = 2 × 345 + 8 × 410 + 5 × 498 – 6 × 804 – 8 × 464 = –2076
rH1 + 4 × 41 = –2076 – 3 × 143= –2669 kJ/mol
26. (i) HCl + NaOH ⎯→ NaCl + H2O rH1 = –13680 cal

(ii) NH4OH + HCl ⎯→ NH4Cl+ H2O rH2 = –12270 cal
(iii) NH4Cl + NaOH ⎯→ NH4OH + NaCl rH3 = ?
(iii) = (ii) – (i)
rH3 = rH2 – rH1= –12270 + 13680= +1410 cal
27. H+ + OH– ⎯→ H2O H° = –57 kJ/mol

H ion HCN = 45 kJ/mol
Ba(OH) 2 + HCN
20m mol 50m mol
⎯→
m mol of H+ = 50 ; m mol OH– = 40
APNI KAKSHA 63
Hneut = –57 × 0.04 + 45 × 0.04 = –12 × 0.04 kJ = –480 J

500  2.11.2
28. q= kJ (for 80 m mole)
1000
500  2.11.2
q= (for 1 mole)
1000  0.08
= + 31.5 kJ mol–1
29. Na2CO3 + CaCl2 ⎯→ CaCO3  + 2NaCl
rH = Hƒº CaCO3 – Hƒ Ca2+ – Hƒ CO32–
= –288 + 129 + 161= + 2 kcal/mol
30. H500K – H298K = (CP)r (500 – 298)

(CP)r = = 37 + 29 – 33 – 29 = 4 J/mol K
rH = –393 + 241 + 110 = 351 – 393 = –42 kJ/mol
4  302
H500K – (–42) =
1000
4  202
H500K = –42 + = – 41.192 kJ/mol
1000
1 1
31. H2 + I2(g) ⎯→ HI(g)
2 2
(Cp)r = –2 × 10–3T
400
rH 400K – rH 300K = ∫300 𝐶𝑝𝑑𝑇
400
rH 400K – (–8000) = –2 × 10–3∫300 𝑇𝑑𝑇
rH 400K = –8000 – 70 = –8070 cal

32. (i) rH° = Hf CO2(g) – Hf H2O(g) – Hf CO(g)
= – 94 + 57 + 26= – 11 Kcal mol–1
(ii) rG° 298K = –94 + 32 + 54= –8 Kcal/mol
(iii) rS°298K
G° = H° – T S°
–8 = –11 – 298 × S°
298 × S° = –3
APNI KAKSHA 64
3
S° = − × 1000 = –10.067 Cal K–1 mol–1
298
– 10.067 = 31 + SH2O – 47.51
SH2O = 56.933 Cal K–1 mol–1
(iv) H = U + ngRT
U = –11 Kcal/mol
33. rH° = – 75 – 392 + 484 = + 17 kJ/mol
G° = H° – TS°
for a process to be spontaneous
 H  17  1000
S° = = = 200 Jmol–1 K–1
T 85
1
34. C(s) + O2(g) ⎯→ CO(g) H = –110 kJ
2
C(s) + H2O(g) ⎯→ CO(g) + H2(g) H = +130 kJ
To keep the temp of reaction constant
220 x = 130 y
x/y = 0.6
EXERCISE O-II
3. H2(g) ⎯→ 2H(g)
rH = H atom. H2(g) = 2 Hƒ H(g) = H – H
1
H2(g) + 2O2(g) ⎯→ H2O()
rH = Hƒ N2O() = Hc H2(g)

4. (A) rHº = Hƒº P – Hƒº R
(B) C (graphite, s) + O2(g) ⎯→ CO2(g)
rHº = Hƒº CO2(g) = Hcº C(graphite, s)
(C) G = H – TS
(D) N2(g) + O2(g) ⎯→ 2NO(g)
 ng = 0
 H = U
5. HC 1-butene = – 649.8 kcal/mol (from iv)
HC trans-2-butene = – 647.0 kcal/mol (from v)
1-butene ⎯→ trans-2-butene rH = –2.8 kcal/mol
APNI KAKSHA 65
Cis-2-butene ⎯→ trans-2-butene H1 from (i)

Cis-2-butene ⎯→ 1-butene H2 from (ii)
1-butene ⎯→ trans-2-butene H1 – H2 = –2.8
from (v) 9H1 + 5H2 = 0
H1 = –1.0 kcal/mol
H2 = 1.8 kcal/mol
6. H – H = 436 kJ/mol and O = O = 495 kJ/mol

1
(A) H2O(g) ⎯⎯→
242
H2(g) + O2(g)
2
0  436  495/2
rH
H2O(g) ⎯⎯⎯
2
→ 2H(g) + O(g)
495
rH2 = 242 + 436 +
2
2 O – H = 925.5 kJ/mol
(B) OH(g) ⎯→ H(g) + O(g)
rH = O – H = 462.75 kJ/mol
H − H 436
(C) Hƒ H(g) = = = 218 kJ/mol
2 2
(D) Hƒ OH(g) = 42 kJ/mol
8. H2S(g) ⎯→ H(g) + HS(g)

rH = Hƒ HS(g) + Hƒ H(g) – Hƒ H2S(g)
376 = Hƒ HS(g) + 218 + 20

Hƒ HS(g) = 138 kJ/mol
9. HS(g) ⎯→ H(g) + S(g)
rH =S– H = 218 + 277 – 138 = 357 kJ/mol
10. C (graphite, s) + O2(g) ⎯→ CO2(g)

−591
rH =  12 = – 394 kJ
18
APNI KAKSHA 66
11. C6H6() + O2(g) ⎯→ 6CO2(g) + 3H2O()
rH = – 6 × 394 – 3 × 286 – 50 = – 3272 kJ
12. (A) C (graphite, s) + O2(g) ⎯→ CO2(g)

rHº = Hºƒ CO2(g) = Hºc C (graphite, s)
(B) C (graphite, s) ⎯→ C(gas)
rHº = Hº atom. = Hº sub.
(C) CH3COOH(aq) + OH– (aq) ⎯→ CH3COO– (aq) + H2O()
rHº = Hº neat.
(D) CH4(g) = C(g) + 4H(g)
rHº = Hº atom. CH4(g) = 4 C – H
13. (P) O2(g) Hƒº = 0 ; ƒSº = 0

(Q) O3(g) Hƒ = + ve ; ƒSº = –ve
2
O2(g) ⎯→ O3(g) rH = +ve
3
(R) Br2() ⎯→ Br2(g) rH = +ve
Sƒº = +ve
(S) H2(g) ⎯→ H2() rH = – ve
Sƒ = – ve
14. (P) for 5 × 32 g O2  H = – 2601 kJ

−285.8
for 16 g O2  H = –  16 = – 260.1 kJ
5  32
(Q) for 16 g O2  rH = – 285.8 kJ
(R) for 16 g O2  rH = – 302.4 kJ
(S)  for 32 g O2  rH = – 393.5 kJ
−393.5
 for 16 g O2  rH = = – 196.75 kJ
2
APNI KAKSHA 67
EXERCISE S-II
1. Fe2O3 + 2Al ⎯→ Al2O3 + 2Fe
rHº = Hƒº Al2O3 – HƒºFe2O3= – 399 + 199 = – 200 kcal / mol
if Fe2O3 and Al are taken in stoichiometric ratio then 1 mol of Fe2O3 react with 2 moles of Al
 160 g of Fe2O3 + 54g Al2O3 react to produce = 200 kcal heat
200
 heat produced per gram = = 0.9345 Kcal g–1
204
160 54
Total vol. = + = 50.77 mL
5.2 2.7
200
Heat produced per mL = = 3.94 Kcal mL–1
50.77
rH
2. C2H5OH(l) ⎯⎯⎯ → CH3–O–CH3 (l)
CH3–O–CH3(l) + 3O2(g) ⎯→ 2CO2(g) + 3H2O(l)
–348 = 2Hf CO2(g) + 3Hf H2O(l) – Hf CH3–O–CH3
Hf CH–O–CH3 = –2 × 94 – 3 × 68 + 348= –44 Kcal mol–1
rH = –44 + 66= 22 kcal mol–1
3. C2H2(g) + O2(g) ⎯→ 2CO2(g) + H2O()
– 312 = 2 Hƒ CO2(g) + Hƒ H2O () – Hƒ C2H2(g)
Hƒ C2H2(g) = – 2 × 94 – 68 + 312 = 56 kcal
2C(graphite, s) + H2(g) ⎯⎯ → C2H2(g)

56
 2×150   0
2C(g) + 2H(g) ⎯→ C2H2(g)
56 = 2 × 150 + 103 – 2 × 93 – C  C
C  C = 161 kJ/mol
1
4. HgO(s) ⎯→ Hg(s) + O2(g)
2
rH° = – H 0f HgO(s) = +90.8
qp = +90.8 kJ/mol–1
rH° = rU° + ng RT
0.5  8.314  298
90.8 = U +
1000
qv = rU° = + 89.56 kJ/mol
at const p
41.84
Moles of HgO(s) reacted = = 0.46
90.8
Moles of Hg(l) formed = 0.46
mass of Hg(l) formed = 0.46 × 200.6= 92.435g
APNI KAKSHA 68
at const. vol.
41.84
Moles of HgO(s) reacted =
89.56
41.84
Moles of Hg(l) formed =
89.56
41.84
Mass of Hg(l) formed =  200.6 = 93.715g
89.56
3
5. B(s) + H2(g) ⎯⎯⎯ 100KJ
→ BH3(g)
2
 565  1.5×436 0
B(g) + 3H(g) ⎯→ BH3(g)
rHº = Hƒº BH3(g) = 100 kJ
100 = 565 + 1.5 × 436 – 3× B – H
3× B – H = 565 + 1.5 × 436 – 100
 B – H = 373 KJ/mol
2B(s) + 3H2(g) ⎯⎯
36
→ B2H6(g)
 2×565  3×436 0
2B(g) + 6H(g) ⎯→ B2H6(g)
rHº = HƒºB2H6(g) = 36 kJ/mol
36 = 2 × 565 + 3 × 436 – 4 × 373 – 2  B – H – B
2  B – H – B = 910 kJ
 B – H – B = 455 kJ/mol
1
6. H2(g) + O2(g) ⎯→ H2O(g)
2
rH = HƒºH2O(g) = – 241.8
– 241.8 = 2 × 218 + 249.2 – 2 O – H
O – H = 463.5 kJ/mol
2  8.314  298
2 × 463.5 = U +
1000
U = 922 (for 2 O – H bond)

922
= (for 1 O – H bond) = 461 kJ/mol
2
APNI KAKSHA 69
7. 2C(g) + 6H(g) ⎯→ C2H6(g)
2840 =  C – C + 6 C – H
2C(g) + 2H(g) ⎯→ C2H4(g)
2275 = C = C + 4 C – H
if  C – H = 410 kJ/mol
then  C – C = 380 kJ/mol
 C = C = 635 kJ/mol
– 5505 + RE = – 5530  RE = – 25 kJ/mol
3 rH1
8. CH3OH () + O2(g) ⎯⎯⎯ → CO2(g) + 2H2O ()
2
R.H.
 35.5   –143  2×40.6
3 rH2
CH3OH(g) + O2(g) ⎯⎯⎯ → CO2(g) + 2H2O(g)
2
rH1 + 2 × 40.6 = rH2 + 35.5 – 143

3
rH2 = 3 C – H + C – O + O – H + O= O – 2 C = O – 4 O – H
2
3
= 3 × 414 + 351.5 + ×494 – 2 × 7.11 – 3 × 464.5 = – 481
2
rH1 + 2 × 40.6 = – 481 + 35.5 – 143
rH1 = – 669.7 kJ/mol
APNI KAKSHA 70
EXERCISE JEE-MAIN
1. rH = C – C + H – H – C – C – 2 C – H
= 615 + 435 – 347 – 2 × 414= – 125 kJ
2. C (graphite, s) + O2(g) ⎯→ CO2(g)

rH = – 393.5
1
CO(g) + O2(g) ⎯→ CO2(g)
2
rH = – 283 kJ
– 283 = – 393.5 – Hƒ CO(g)
Hƒ CO(g) = – 110.5 kJ
1 1
3. X2(g) + Y2(g) ⎯→ XY(g)
2 2
1 1
rH = X – X + Y – Y – X – Y
2 2
1 1
– 200 = × a + × 0.5a – a
2 2
A = X – X = 800
1 1 rH1
4. I2(s) + Cl2(g) ⎯⎯⎯ → ICl(g)
2 2
 62.76/2  0 0
1 1 rH2
I2(g) + Cl2(g) ⎯⎯⎯ → ICl(g)
2 2
62.76
rH2 + = rH1
2
1 1
rH2 = × 151 + × 242.3 – 211.3 = 196.65 – 211.3 = – 14.65
2 2
62.76
rH1 = – 14.65 + = 16.73 kJ/mol
2
5. C (graphite) + 2H2(g) ⎯→ CH4(g)
1
6. rH = × 240 – 349 – 381= – 610 kJ/mol
2
APNI KAKSHA 71
7. rGº = – 394.4 – 2 × 237.2 + 166.2
= – 702.6 kJ/mol
= W non – PV
H = – 726 kJ/mol = q
465.4
= 100  97%
726
8. 57.32 = Hƒ OH– (aq) – Hƒ H2O()

57.32 = Hƒ OH– (aq) + 286.2
Hƒ OH– (aq) = – 228.88 kJ
1 3
9. N2(g) + H2(g) ⎯→ NH3(g)
2 2
3 1
– 46 = × 436 + × 712 – 3 N – H
2 2
3 N – H = 1056   N – H = 352 kJ mol–1
10.
rH + 2 × 54 = – 111rH = – 219 kJ
11. – 51.46 = – 55.90 + H ion

H ion. = + 4.44 kJ mol–1
1 −617
12. Li(s) + F2(g) ⎯⎯⎯ → LiF(s)
2
 161  77
Li(g) F(g) –1047
 520  egH
Li+(g) + F–(g)
161 + 520 + 77 + egH F(g) – 1047 = – 617
egH F(g) = –328 kJ/mol
13. H2O() ⎯→ H2O(g)

rH = b – a = – 241.8 + 285.9 = + 44.1 kJ
APNI KAKSHA 72

rH = H sub. C(graphite) + 2 H – H – 4 C – H
15. C2H5OH() + 3O2(g) ⎯→ 2CO2(g) + 3H2O()

U = – 1364.47 kJ/mol
1 8.314  298
= – 1364.47 – = – 1366.95 kJ/mol
1000
16. 4 C – H = 360 kJ
C – H = 90 kJ/mol
C – C + C – H = 620
80
C – C = 80 kJ/mol = ev / bond
96.5
1240
 =  96.5 nm = 1.493 × 03 nm
80
17. (i) C (graphite) + O2(g) ⎯→ CO2(g)

H = – 393.5 kJ mol–1
1
(ii) CO(g) + O2(g) ⎯→ CO2(g)
2
H = – 283.5 kJ/mol
1
(iii) C (graphite) + O2(g) ⎯→ CO(g)
2
(iii) = (i) – (ii)
rH = – 393.5 + 283.5 = –110.0 kJ/mol

rH = Hƒ CH4(g)
890.3 = Hƒ CH4(g) – Hƒ CO2(g) – 2 Hƒ H2O()
890.3 = Hƒ CH4(g) + 393.5 + 2 × 285.8

rH = Hƒ CH4(g) = – 74.8 kJ/mol
19. C6H6() + 7.5 O2(g) ⎯→ 6CO2(g) + 3H2O()

ng = – 1.5
APNI KAKSHA 73
1.5  8.314  298
H = – 3263.9 – = –3267.6 kJ
1000
20. (i) C (graphite) + O2(g) ⎯→ CO2(g)

rHº = x kJ/mol
1
(ii) C (graphite) + O2(g) ⎯→ CO(g)
2
rHº = y kJ/mol
1
(iii) CO(g) + O2(g) ⎯→ CO2(g)
2
rHº = 2 kJ/mol
(i) = (ii) + (iii) x = y + z
21. I2(s) ⎯→ I2(g)

( Cp)r = 0.031 – 0.055 = – 0.024 cal g–1 k–1
rH 523 k – rH 473 k = – 0.024 × (523 – 473)
rH 523 k – 24 = – 0.024 × 50
rH 523 k = 22.8 cal g–1
22. H2 O(I) → H2 O(g)
ΔHvap = ΔU + Δng RT
ΔU = ΔHvap − RT
= 41,000 − 8.314 × 373Jmol−1
= 37898.878
For 5moles, ΔU = 37898.878 × 5 J = 189494 J
23. ΔSol H ∘ = Δlattice H ∘ + ΔHyd H ∘
4 = 788 + ΔHyd. H ∘
ΔHyd H ∘ = −784 kJ/mol
24. 𝐴 + 𝐵𝑂2 → 𝐵 + 𝐴𝑂2
Δ𝐺 = −𝑣𝑒
APNI KAKSHA 74
Only above 1400∘ C
25. According to the given data of I.E,

This element must belong to group 1 and thus is monovalent and form hydroxide of the type
𝑀(𝑂𝐻).
MOH + HCl → MCl + H2 O
1 mole 1 mole
2MOH + H2 SO4 → M2 SO4 + H2 O
1 mole 1/2 mole

1
27.  f H KCl =  sub H (K
 
) +  ionization H (K ) +

 bond H (Cl 2)
+electron gain H(Cl) + lattice H(KCl)

2
1
 – 436.7 = 89.2 + 419.0 + (243.0) + {–348.6} + lattice H(KCl)

 lattice H(KCl) = −717.8kJ mol−1
The magnitude of lattice enthalpy of KCl in kJ mol–1 is 718 (Nearest integer).

28. H =HCombustion (Reactant) – HCombustion
(Product)
= 3 × (–1300) – [–3268]
= – 632 kJ mol –1
29. C(s) + O2(g) → CO2 (g) ; H = – x kJ/mole
Q = CT = 20 kJ × 2
40 kJ heat is released for 2.4 g of C
40
For 1 mole ‘C’ : Q =  12
2.4
400
=  12 = 200 kJ/mole
24
Q=E = H = 200 kJ ( ng = 0)
x = 200
30. Hionisation of CH3COOH = | – 57.3 – (– 55.3)|
= 2 kJ/mol
31. HNO3 NaOH
APNI KAKSHA 75
600 mL × 0.2 M 400 mL × 0.1 M
= 120 m mol = 40 m mol
HNO3 + NaOH → NaNO3 + H2O
Bef. 120 40
Aft. 80 0 40 m mol
(
Δ r H = 40mmol  57 103 ) mol
J
J
= 40  10 −3 mol  57 103
mol
=2280 J
mST = 2280
1gm
 1000mL   4, 2  ΔT = 2280
mL
2280
ΔT =  10 −3
4.2
22800
=  10 −3 = 542.86 10−3
42
ΔT = 54.286 10−2 K
ΔT = 54.286 10−20 C
Ans. 54.286
Answer mentioned as 54 (Closest integer)
APNI KAKSHA 76
EXERCISE JEE-ADVANCE
−1100
1. S(s) + 3F2(g) ⎯⎯⎯ → SF6(g)
 275  6×80 0
S(g) + 6F(g) ⎯→ SF6(g)
– 1100 = 275 + 6 × 80 – 6 S – F
6 S – F = 275 – 6 × 80 + 1100
S – F = 309.16 kJ/mol
2. Combination is exothermic reaction
3. rH = Hƒ B2O3(s) + 3Hƒ H2O(g) – Hƒ B2H6(g)
Hƒ B2O3(s) = – 1273 kJ
44 = Hƒ H2O(g) + 286
Hƒ H2O(g) = – 242 kJ
Hƒ B2H6 = 36 kJ
rH = – 1273 – 3 × 242 – 36= – 2035 kJ/mol
4. rH = Hƒ CO(g) + Hƒ H2O(g) – Hƒ CO2(g)

= – 110.5 – 241.8 + 393.5 = 41.2 kJ/mol
6. 9 = 2.5 × 0.45 kJ
2.5  0.45
H = −  28 = – 9 kJ/mol
3.5
7. 2C(s) + H2(g) ⎯→ C2H2(g) H = 225 kJ /mol
 1410  330 0
2C(g) + 2H(g) ⎯→ C2H2(g)
225 = 1410 + 330 – 2 × C – H – C  C
225 = 1740 – 2 × 350 – C  C
C  C = 1740 – 700 – 225 = + 815 kJ
8. C6H12O6(s) + 6O2(g) ⎯→ 6CO2(g) + 6H2O()
rH = – 6 × 400 – 6 × 30 + 1300

= – 2700 kJ/mol
2900
=− kJ (per gram) = – 16.11 kJ
180
APNI KAKSHA 77
10. SnO2 ( s) + C(s) ⎯→ CO2 + Sn

∆H = (∆f H)P − (∆f H)R
= −394 + 581
= +187KJ/mol
∆S = (∆S)P − (∆S)R
= 210 + 52 − 56 − 6
= 200 J/kmol
∆G = 187 × 1000 − 200 × T
T = [187 × 1000]/200 = 935 K
11. 2Hg(g) + O2 ( g) − 2HgO(s)
Heat capacity of calorimeter = 20 kJ K −1
Rise in temperature = 14.8 K
Heat evolved = 20 × 14.8 = 296 kJ
ΔH ∘ = ΔU ∘ + Δng RT
= −296 − 3 × 8.3 × 298 × 10−3
≃ −303.42 kJ
ΔH ∘ = ΔHfo (HgO(s)) − ΔHfo (Hg(g))
−303.42 = ΔHfo (HgO(s)) − 2 × 61.32
ΔHfo (HgO(s)) = −303.42 + 122.64
= −180.78 kJ
|ΔHfo (HgO(s))| = 90.39 kJ mol−1
APNI KAKSHA 78

Sheet - 01 - Thermochemistry

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Sheet - 01 - Thermochemistry

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(Physical Chemistry) THERMOCHEMISTRY

1. Why does heat get released/absorbed during chemical reactions?

3. FACTORS AFFECTING H OF THE REACTIONS ARE :

= Difference in molar heat capacities of products and reactants.

* for a constant volume reaction, E02 = E10 +   r CV .dT

(A)  r H 300 >  r H 310

5. TYPES OF ENTHALPY CHANGES IN CHEMICAL REACTIONS :

5.1 STANDARD ENTHALPY OF FORMATION :

5.1.1 ENTHALPY OF REACTION FROM ENTHALPIES OF

5.1.2 HESS’S LAW OF CONSTANT HEAT SUMMATION :

4. Calculate heat of the following reaction at constant pressure,

5. If H2 + 1/2 O2 ⎯→ H2O, H = – 68 kcal

5.2 STANDARD ENTHALPY OF COMBUSTION :

5.1.2 MEASUREMENT OF ENTHALPY OF COMBUSTION :

due to 1 mole, heat released =   q = UC°

Sol. + O2 → CO2 + H2O

volume of C2H4 in a 1 litre mixture = 2/4 = 0.5 lit.

5.3 INTEGRAL ENTHALPY OF SOLUTION :

5.3.1 ENTHALPY OF HYDRATION :

5.3.2 ENTHALPY OF HYDRATION OF GASEOUS IONS :

Cl¯(g) + aq. —→ Cl¯(aq) Hr° = Hf° (Cl–, aq)

5.1.3 ENTHALPY OF FORMATION OF IONS :

Sol. For the reaction, HCl(g) + aq ⎯→ H+(aq) + Cl¯(aq)

5.4 ENTHALPY OF NEUTRALIZATION :

H+(aq) + OH¯(aq) —→ H2O() H= –57.1 kJ/mole = –13.7 kcal/mol

5.4.1 ENTHALPY OF IONIZATION :

Hence fH (OH¯, aq) = fH(H2O, ) – neutH

5.5 ENTHALPY OF TRANSITION :

5.6 ENTHALPY OF PRECIPITATION :

1. Benzene burns according to the following equation at 300 K (R = 25/3 J mole–1K–1)

5.5 BOND ENTHALPIES :

 Estimation of Enthalpy of a reaction from bond Enthalpies :

Data : Bond Bond enthalpy

Hr = (4HC–H + HC=C + HH–H) – (6HC–H + HC–C)

Data Bond enthalpy of C – H bond = 413.38 kJ mol–1

Method-1 For which energy released is

But we want fH corresponding to the following equation

This can be obtained by the following manipulations :

Method-2 Diagrammatically, the above calculations may be represented as follows.

Applying Hess’s law, we get

= (5 x 718.39 + 4 x 435.97 – 2 x 615.05 – 2 x 347.69 – 8 x 413.38) kJ mol–1

5.7 Resonance Energy :

2. Calculate Hºr for the reaction CH2Cl2 (g) ⎯⎯

3. Calculate the enthalpy change (H) of the following reaction

2C2H2(g) + 5O2(g) ⎯⎯ → 4CO2(g) + 2H2O(g) given average bond enthalpies of various

6. Ethanol can undergoes decomposition to form two sets of products.

7. Find the bond enthalpy of S – S bond from the following data :

1.5  8.314  300

Hr = 2HC–H + 2HC–Cl = 2 × 414 + 2 × 330 = 828 + 660 = 1488 kJ/mol.

Hr = 2[HC  C+ 2HC–H ] + 5 HO = O – 4 [2HC = O] –2 [2HO–H ]

3. Using the following information calculate the heat of formation of CH4.

4. The standard enthalpy of formation of ammonia gas is -

H f [N2H4(g)] = – 120kJ /mol

(A) –60 kJ (B) –180 kJ (C) 40 kJ (D) –80 kJ

6. NH3(g) + 3Cl2(g) → NCl3(g) + 3HCl (g); –H1

7. Study the following thermochemical equations :

(A) 212.2 kJ (B) – 143.3 kJ (C) 185.4 kJ (D) – 103.6 kJ

ENTHALPY OF REACTION AND RELATION BETWEEN H AND U

13. The enthalpy changes of the following reactions at 27°C are

14. 2NO2(g) → N2O4(g)

BOND ENTHALPY , ENTHALPY OF ATOMISATION, ENTHALPY OF VAPOURISATION

Bond Bond Enthalpy kcal

HYDRATION ENTHALPY, ENTHALPY OF SOLUTION, HYDRATION AND DILUTION